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METAL-CATALYZED ALKOXYCARBONYLATION OF A LACTONE

20180265449 ยท 2018-09-20

    Inventors

    Cpc classification

    International classification

    Abstract

    The metal-catalyzed alkoxycarbonylation of a lactone is a method of alkoxycarbonylating a -lactone, specifically 3-ethylidene-6-vinyltetrahydro-2H-pyran-2-one. The method includes combining the -lactone with an alcohol in an organic solvent in the presence of a catalyst system that includes palladium or a salt thereof to form a reaction mixture, which is heated to 110-130 C. at a pressure of 20-50 bar for between 3-5 hours under flow of carbon monoxide gas. The product of the reaction is a substituted 2-octendioate diester. The alcohol may be methyl alcohol, n-butyl alcohol, 2-ethylhexanol, isobutyl alcohol, isopropyl alcohol, benzyl alcohol, or phenol. The solvent may be toluene, acetonitrile, or tetrahydrofuran. The method may include adding an acid to the reaction mixture, which may be dilute (about 5 mol %) sulfuric or p-toluenesulfonic acid. The catalyst system may also include a phosphine ligand.

    Claims

    1. A method for metal-catalyzed alkoxycarbonylation of a -lactone, the -lactone being 3-ethylidene-6-vinyletetrahydro-2H-pyran-2-one, the method comprising the steps of: adding an alcohol and a catalyst system including palladium or a salt thereof to a solution of the -lactone in an organic solvent to form a reaction mixture; placing the reaction mixture under pressure of carbon monoxide (CO) gas; heating the reaction mixture to a temperature of at least 110 C.; and recovering a 2-octendioate diester product.

    2. The method for metal-catalyzed alkoxycarbonylation according to claim 1, wherein the catalyst system further comprises a phosphine ligand.

    3. The method for metal-catalyzed alkoxycarbonylation according to claim 2, wherein the phosphine ligand is selected from the group of phosphine ligands having the formulas shown in L1, L2, L3, L4, L5, L6, L7, L8, L9, L10, L11, L12, L13, L14, L15, L16, L17, L18, L19, L20, and L21 of FIGS. 6A, 6B, and 6C.

    4. The method for metal-catalyzed alkoxycarbonylation according to claim 2, wherein the phosphine ligand has the formula: ##STR00006##

    5. The method for metal-catalyzed alkoxycarbonylation according to claim 2, further comprising the step of adding an acid to the reaction mixture.

    6. The method for metal-catalyzed alkoxycarbonylation according to claim 5, wherein the acid is selected from the group consisting of p-toluenesulfonic acid, methanesulfonic acid, hydrochloric acid, and sulfuric acid.

    7. The method for metal-catalyzed alkoxycarbonylation according to claim 5, wherein the acid is p-toluenesulfonic acid.

    8. The method for metal-catalyzed alkoxycarbonylation according to claim 5, wherein the acid is sulfuric acid.

    9. The method for metal-catalyzed alkoxycarbonylation according to claim 5, wherein the acid is diluted to 5 mol %.

    10. The method for metal-catalyzed alkoxycarbonylation according to claim 1, wherein the solvent is selected from the group consisting of toluene, acetonitrile, and tetrahydrofuran.

    11. The method for metal-catalyzed alkoxycarbonylation according to claim 1, wherein the step of heating the reaction mixture comprises heating the reaction mixture to 110-130 C.

    12. The method for metal-catalyzed alkoxycarbonylation according to claim 1, wherein the step of placing the reaction mixture under pressure carbon monoxide gas comprises placing the reaction mixture under pressure of at least 20 bar CO.

    13. The method for metal-catalyzed alkoxycarbonylation according to claim 12, wherein the pressure is 20-50 bar CO.

    14. The method for metal-catalyzed alkoxycarbonylation according to claim 1, wherein the step of heating the reaction mixture is carried out for at least three hours.

    15. The method for metal-catalyzed alkoxycarbonylation according to claim 1, wherein the step of heating the reaction mixture is carried out for three to five hours.

    16. The method for metal-catalyzed alkoxycarbonylation according to claim 1, wherein the alcohol is selected from the group consisting of methyl alcohol, n-butyl alcohol, 2-ethylhexanol, isobutyl alcohol, isopropyl alcohol, benzyl alcohol, and phenol.

    17. The method for metal-catalyzed alkoxycarbonylation according to claim 1, further comprising the step of heating the 2-octendioate diester product in tetrahydrofuran solvent in the presence of a Pd/C catalyst and under flow of hydrogen gas in order to obtain a saturated diester product.

    18. The method for metal-catalyzed alkoxycarbonylation according to claim 1, further comprising the step of reacting the 2-octendioate diester product with bis(trifluoromethane)sulfonimide (HNTf.sub.2) in the presence of ruthenium acetylacetonate/1,1,1-tris-(diphenylphosphinomethyl)ethane catalyst under pressure of hydrogen gas to obtain a saturated diol product.

    19. An alkoxycarbonylated -lactone having the formula: ##STR00007## wherein R is selected from the group consisting of methyl, n-butyl, 2-ethylhexanyl, isobutyl, isopropyl, benzyl, and phenyl.

    Description

    BRIEF DESCRIPTION OF THE DRAWINGS

    [0013] FIG. 1 is a reaction scheme for the metal-catalyzed alkoxycarbonylation of a lactone, specifically 3-ethylidene-6-vinyltetrahydro-2H-pyran-2-one.

    [0014] FIG. 2 is a reaction scheme for the synthesis of 3-ethylidene-6-vinyltetrahydro-2H-pyran-2-one using carbon dioxide according to the prior art.

    [0015] FIG. 3 is a multi-step reaction scheme for the alkoxycarbonylation of 3-ethylidene-6-vinyltetrahydro-2H-pyran-2-one to form a diester.

    [0016] FIG. 4 is the reaction scheme for the metal-catalyzed alkoxycarbonylation of 3-ethylidene-6-vinyltetrahydro-2H-pyran-2-one using any one of five alcohols.

    [0017] FIG. 5 is a reaction scheme used in experiments for determining the effect of a ligand attached to the palladium catalyst.

    [0018] FIGS. 6A, 6B, and 6C show the ligands used in determining the effect of ligands in the reaction scheme of FIG. 5.

    [0019] FIG. 7 shows the reaction scheme used in determining the effect of the acid in the reaction scheme of FIG. 1.

    [0020] FIG. 8 shows the reaction scheme used in determining the effect of the solvent in the reaction scheme of FIG. 1.

    [0021] FIG. 9 shows the reaction scheme used in determining the effect of the palladium precursor in the reaction scheme of FIG. 1.

    [0022] FIG. 10 shows the reaction scheme used in determining the effect of the acid and methanol amounts in the reaction scheme of FIG. 1.

    [0023] FIG. 11 shows the reaction scheme used in determining the effect of the pressure in the reaction scheme of FIG. 1.

    [0024] FIG. 12 shows the reaction scheme used in determining the effect of the temperature in the reaction scheme of FIG. 1.

    [0025] FIG. 13 shows the reaction scheme used in determining the effect of the alcohol scope in the reaction scheme of FIG. 1.

    [0026] FIG. 14 is a first reaction scheme for further hydrogenating a diester obtained from the reaction scheme of FIG. 4.

    [0027] FIG. 15 is a second reaction scheme for further hydrogenating the diester obtained from the reaction scheme of FIG. 4, resulting in formation of a saturated diester.

    [0028] FIG. 16 is a third reaction scheme for further hydrogenating the diester obtained from the reaction scheme of FIG. 4, resulting in formation of a diol.

    [0029] FIG. 17 is the structural formulas of various ruthenium additives tested in the reaction scheme of FIG. 16.

    [0030] Similar reference characters denote corresponding features consistently throughout the attached drawings.

    DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

    [0031] The metal-catalyzed alkoxycarbonylation of a lactone is a method of alkoxycarbonylating a -lactone, specifically 3-ethylidene-6-vinyltetrahydro-2H-pyran-2-one. The method includes combining the -lactone with an alcohol in an organic solvent in the presence of a catalyst system that includes palladium or a salt thereof to form a reaction mixture, which is heated to 110-130 C. at a pressure of 20-50 bar for between 3-5 hours under flow of carbon monoxide gas. The product of the reaction is a substituted 2-octendioate diester. The alcohol may be methyl alcohol, n-butyl alcohol, 2-ethylhexanol, isobutyl alcohol, isopropyl alcohol, benzyl alcohol, or phenol. The solvent may be toluene, acetonitrile, or tetrahydrofuran. The method may include adding an acid to the reaction mixture, which may be dilute (about 5 mol %) sulfuric or p-toluenesulfonic acid. The catalyst system may also include a phosphine ligand.

    [0032] The diesters produced from the method described herein may be used as monomers in polymerization reactions typical of olefins and ,-unsaturated esters (e.g., acrylic acid derivatives), including use as co-monomers in combination with other olefins, diamines, or dialcohols to respectively give polyolefins, polyesters, and polyamides. Furthermore, the diesters of 7-ethylideneoct-3-enedioic acid or their saturated derivatives can find application as plasticizers or lubricants. In addition, the diesters of 7-ethylideneoct-3-enedioic acid or their saturated derivatives can be further used for the synthesis of 2-ethyloctane-1,8-diol, which is relevant as a monomer in polyester and polyurethane production.

    [0033] As noted above, the method was developed to help make the -lactone 1 produced by telomerization of butadiene and carbon dioxide (see the reaction scheme in FIG. 2) more commercially attractive, thereby promoting the telomerization reaction as a green chemistry method of turning carbon dioxide waste material into a renewable resource. The inventors first attempted alkoxycarboxylation of the -lactone 1 by heating the lactone 1 in toluene solvent with a primary alcohol and an acidic promoter. Surprisingly, it was found that this reaction produced a mixture of esters, even in the presence of palladium chloride catalyst. The reaction could be made to produce a diester product 2, but only in a multi-step reaction scheme involving alcoholysis/allylic substitution/carbonylation, as shown in FIG. 3. However, this reaction scheme is inefficient and produces unwanted byproducts.

    [0034] In order to develop a more efficient method for direct alkoxycarboxylation of 3-ethylidene-6-vinyltetrahydro-2H-pyran-2-one (the -lactone 1), the inventors attempted using various phosphine ligands in combination with palladium chloride as the precursor catalyst. It was determined that phosphine ligand L11 produced the best selectivity and greatest yield (see the reaction scheme in FIG. 4). As the following data show, the inventors then tested the effect of various reaction conditions (temperature, pressure, acid promoter, palladium precursor, primary alcohol, etc.) to optimize reaction conditions. It was concluded that the reaction scheme shown in FIG. 4 produced the desired diester product 2 in greatest yield with best selectivity in a one-step, one-pot reaction without the production of any by-product but water, thereby providing an economical method of producing intermediates used in the commercial production of valuable polymers.

    [0035] In the examples that follow, all commercial reagents were ordered from Alfa Aesar, Aldrich, TCI, or Strem. Unless otherwise stated, commercial reagents were used without purification. 6-Lactone 1 was synthesized as previously reported in Sharif et al. (Efficient and selective Palladium-catalyzed Telomerization of 1,3-Butadiene with Carbon Dioxide. ChemCatChem 2017) and kept under Ar atmosphere after distillation. Toluene, THF, acetonitrile, and methanol were collected from the solvent purification system and used under standard Schlenk technique. n-Butanol, 2-ethylhexanol, benzyl alcohol, and i-propanol were dried using standard techniques and kept under Ar atmosphere. Analytical data of literature-known compounds were in accord with reported data.

    [0036] NMR spectra were recorded on Bruker AV-300, Bruker Fourier 300, or Bruker AV-400 NMR spectrometers. Multiplets were assigned as s (singlet), d (doublet), t (triplet), dd (doublet of doublet), m (multiplet), and br. s (broad singlet). All measurements were carried out at room temperature, unless otherwise stated. Mass spectra were recorded on an Agilent 6890/5973 GC-MS. High resolution mass spectra (HRMS) were recorded on Agilent 6210 Time-of-Flight LC/MS (Agilent) with electrospray ionization (ESI). The data are given as mass units per charge (m/z) and intensities of signals are given in brackets. For GC analyses, Agilent HP-7890A chromatograph equipped with a FID instrument and a HP-5 column (polydimethylsiloxane with 5% phenyl groups, 30 m, 0.32 mm i.d., 0.25 m film thickness) was used. Unless otherwise stated, the products were isolated from the reaction mixture by column chromatography on silica gel 60, 0.063-0.2 mm, (Merck) using gradient elution from heptane to heptane/AcOEt=8:2.

    Example 1

    GC for Five Alcohols

    [0037] This example provides gas chromatography results for the separation of E/Z stereoisomer products for five alcohols (methyl alcohol, isopropyl alcohol, n-butyl alcohol, 2-ethylhexyl alcohol, and benzyl alcohol) reacted with the -lactone 1 under the conditions shown in the reaction scheme shown in FIG. 4. Gas chromatographic analysis was performed using the following methods.

    [0038] Method 1 is an oven temperature program: 50 C.; 15 C./min to 260 C., 6 min; injection volume 1 L with a split of 50:1. Inlet temperature 200 C.

    [0039] Method 2 is an oven temperature program: 50 C.; 8 C./min to 260 C., 7 min; 8 C./min to 300 C.; injection volume 1 L with a split of 50:1. Inlet temperature 260 C.

    TABLE-US-00002 TABLE 2 Key to GC Entries GC Entry # Alcohol 1 Methyl 2 n-Butyl 3 2-Ethylhexyl 4 Isopropyl 5 Benzyl

    TABLE-US-00003 TABLE 3 Gas Chromatography Retention Time GC GC Retention Entry Method Compound Time (min) 1 1 [00001]embedded image 11.14/11.06 2 1 [00002]embedded image 14.49/14.39 3 2 [00003]embedded image 31.81/31.38 4 1 [00004]embedded image 12.42/12.33 5 2 [00005]embedded image 35.58/35.19

    Example 2

    Spectroscopic Data for Dimethyl 7-Ethylideneoct-3-Enedioate

    [0040] The spectroscopic data for dimethyl 7-ethylideneoct-3-enedioate (the compound shown as Entry No. 1 in Table 3) is the following.

    [0041] .sup.1H NMR (300 MHz, CDCl.sub.3): 6.79 (q, J=7.1 Hz, 1H, E/Z isomers), 5.56-5.38 (m, 2H, E/Z isomers), 3.65 (s, 3H, OCH.sub.3, Z isomer), 3.64 (s, 3H, OCH.sub.3, E isomer), 3.60 (s, 3H, OCH.sub.3, Z isomer), 3.59 (s, 3H, OCH.sub.3, E/Z isomers), 3.00 (d, J=5.9 Hz, 2H, Z isomer), 2.94 (d, J=5.1 Hz, 2H, E isomer), 2.35-2.24 (m, 21-1, E/Z isomers), 2.12-1.97 (m, 2H, E/Z isomers), 1.73 (d, 3H, CHCH.sub.3, Z isomer overlapped with the CHCH.sub.3 signal of E isomer), 1.71 ppm (d, J=7.1 Hz, 3H, CH.sub.3, E isomer).

    [0042] .sup.13C NMR (75 MHz, CDCl.sub.3): 172.4, 172.3 (Z isomer), 168.15, 168.11 (Z isomer), 138.2 (Z isomer), 138.0, 133.8, 132.3, 132.3 (Z isomer), 132.2 (Z isomer), 122.2, 121.6 (Z isomer), 51.82 (Z isomer), 51.76, 51.6, 37.91, 32.7 (Z isomer), 31.8, 26.7 (Z isomer), 26.15, 26.09 (Z isomer), 14.4 (Z isomer), 14.3 ppm.

    [0043] GC-MS-EI m/z (%): 226 (M+, 1), 194 (13), 179 (7), 162 (100), 147 (10), 134 (67), 120 (20), 107 (29), 93 (16), 91 (20), 81 (22), 71 (26), 59 (30).

    [0044] ESI-HRMS calcd for C.sub.12H.sub.18O.sub.4Na [M+Na]+: 249.10973; found: 227.10976.

    Example 3

    Spectroscopic Data for Diisopropyl 7-Ethylideneoct-3-Enedioate

    [0045] The spectroscopic data for diisopropyl 7-ethylideneoct-3-enedioate (the compound shown as Entry No. 4 in Table 3) is the following.

    [0046] .sup.1H NMR (300 MHz, CDCl.sub.3): 6.81 (q, J=7.1 Hz, 1H, E/Z isomers), 5.67-5.33 (m, 2H, E/Z isomers), 5.07-4.86 (m, 2H, E/Z isomers), 3.01 (d, J=5.7 Hz, 2H, Z isomer), 2.94 (d, J=5.2 Hz, 2H, E isomer), 2.38-2.28 (m, 2H, E/Z isomers), 2.20-2.02 (m, 2H, E/Z isomers), 1.76 (d, 3H, CHCH.sub.3, Z isomer overlapped with the CHCH.sub.3 signal of E isomer), 1.74 (d, J=7.1 Hz, 3H, CHCH.sub.3, E isomer), 1.30-0.81 ppm (m, 12H, E/Z isomers).

    [0047] .sup.13C NMR (75 MHz, CDCl.sub.3): 171.5, 167.2, 137.4 (Z isomer), 137.2, 133.6, 132.9, 132.0 (Z isomer), 122.4, 121.9 (Z isomer), 67.8, 67.8, 67.5, 67.4, 38.4, 33.2 (Z isomer), 31.8, 26.8 (Z isomer), 26.2, 26.1 (Z isomer), 21.9, 21.8, 14.3 (Z isomer), 14.3 ppm.

    [0048] GCMS-EI m/z (%): 285 (M+, 0.3), 240 (2), 222 (5), 198 (4), 194 (4), 180 (25), 162 (67), 153 (11), 134 (46), 107 (27), 93 (16), 81 (16), 67 (7), 54 (35), 43 (100).

    [0049] ESI-HRMS calcd for C.sub.16H.sub.26O.sub.4Na [M+Na]+: 305.17233; found: 305.17229.

    Example 4

    Spectroscopic Data for Bis(2-Ethylhexyl) 7-Ethylideneoct-3-Enedioate

    [0050] The spectroscopic data for bis(2-ethylhexyl) 7-ethylideneoct-3-enedioate (the compound shown as Entry No. 3 in Table 3) is the following.

    [0051] .sup.1H NMR (300 MHz, CDCl.sub.3): 6.84 (q, J=7.1 Hz, 1H, E/Z isomers), 5.63-5.33 (m, 2H, E/Z isomers), 4.08-3.89 (m, 4H, E/Z isomers), 3.05 (d, J=5.3 Hz, 2H, Z isomer), 2.99 (d, J=5.3 Hz, 2H, Z isomer), 2.50-2.23 (m, 2H, E/Z isomers), 2.19-2.01 (m, 2H, E/Z isomers), 1.79 (d, 3H, CHCH.sub.3, Z isomer overlapped with the CHCH.sub.3 signal of E isomer), 1.76 (d, J=7.2 Hz, 3H, CHCH.sub.3, E isomer), 1.65-1.44 (m, 2H, E/Z isomers), 1.43-1.12 (m, 16H, E/Z isomers), 0.98-0.77 ppm (m, 12H, E/Z isomers).

    [0052] .sup.13C NMR (75 MHz, CDCl.sub.3): 172.2, 167.8, 137.8 (Z isomer), 137.6, 133.6, 132.6, 132.1 (Z isomer), 122.4, 121.7 (Z isomer), 67.0, 66.6, 38.9, 38.7, 38.2, 33.0 (Z isomer), 31.9, 30.6, 30.4, 28.98, 28.91, 26.8 (Z isomer), 26.3, 26.1 (Z isomer), 24.0, 23.8, 23.0, 14.4 (Z isomer), 14.3, 14.0, 11.1, 11.0 ppm.

    [0053] GCMS-EI m/z (%): 422 (M+, 0.3), 292 (4), 264 (4), 198 (4), 180 (44), 162 (100), 152 (12), 134 (29), 107 (15), 81 (8), 71 (44), 57 (69), 43 (41).

    [0054] EI-HRMS calcd. for C.sub.26H.sub.46O.sub.4 [M]+: 422.33906; found: 422.33917.

    Example 5

    Spectroscopic Data for Dibenzyl 7-Ethylideneoct-3-Enedioate

    [0055] The spectroscopic data for dibenzyl 7-ethylideneoct-3-enedioate (the compound shown as Entry No. 5 in Table 3) is the following.

    [0056] .sup.1H NMR (300 MHz, CDCl.sub.3): 7.39-7.21 (m, 10H, E/Z isomers), 6.92 (q, J=7.1 Hz, 1H, E/Z isomers), 5.67-5.43 (m, 2H, E/Z isomers), 5.16 (s, 2H, E/Z isomers), 5.10 (s, 2H, E/Z isomers), 3.07 (d, J=5.2 Hz, 2H, Z isomer), 3.03 (d, J=4.2 Hz, 2H, E isomer), 2.50-2.30 (m, 2H E/Z isomers), 2.21-2.08 (m, 2H E/Z isomers), 1.75 (d, J=7.1 Hz, 3H, CHCH.sub.3, Z isomer overlapped with the CHCH.sub.3 signal of E isomer), 1.74 ppm (d, J=7.2 Hz, 3H, CHCH.sub.3, Z isomer overlapped with the CHCH.sub.3 signal of E isomer).

    [0057] .sup.13C NMR (75 MHz, CDCl.sub.3): 171.7, 171.6 (Z isomer), 167.3, 138.5 (Z isomer), 138.4, 136.4, 135.9, 133.8, 132.3, 132.2 (Z isomer), 128.5, 128.2, 128.0, 127.9, 122.2, 121.6 (Z isomer), 66.3, 66.1, 38.0, 32.8 (Z isomer), 31.8, 26.8 (Z isomer), 26.1, 26.0 (Z isomer), 14.3 ppm.

    [0058] GCMS-EI m/z (%): 287 (2), 269 (3), 251 (3), 223 (2), 181 (2), 163 (4), 107 (2), 91 (100), 65 (7).

    [0059] ESI-HRMS calcd for C.sub.24H.sub.26O.sub.4Na [M+Na]+: 401.17233; found: 401.17243.

    Example 6

    Spectroscopic Data for Dibutyl 7-Ethylideneoct-3-Enedioate

    [0060] The spectroscopic data for dibutyl 7-ethylideneoct-3-enedioate (the compound shown as Entry No. 2 in Table 3) is the following.

    [0061] .sup.1H NMR (300 MHz, CDCl.sub.3): 6.79 (q, J=7.1 Hz, 1H, E/Z isomers), 5.71-5.27 (m, 2H, E/Z isomers), 4.11-3.92 (m, 4H, E/Z isomers), 2.99 (d, J=5.4 Hz, 2H, Z isomer), 2.93 (d, J=5.1 Hz, 2H, E isomer), 2.31 (t, J=7.6 Hz, 2H, E/Z isomers), 2.16-1.90 (m, 2H, E/Z isomers), 1.73 (d, 3H, CHCH.sub.3, Z isomer overlapped with the CHCH.sub.3 signal of E isomer), 1.70 (d, J=7.2 Hz, 3H, CH.sub.3, E isomer), 1.63-1.45 (m, 4H, E/Z isomers), 1.43-1.15 (m, 4H, E/Z isomers), 0.86 ppm (m, 6H, E/Z isomers).

    [0062] .sup.13C NMR (75 MHz, CDCl.sub.3): 171.9, 171.8 (Z isomer), 167.6, 137.6 (Z isomer), 137.4, 133.5, 132.6, 132.5 (Z isomer), 132.0 (Z isomer), 122.3, 121.7 (Z isomer), 64.3, 64.1, 38.1, 32.8 (Z isomer), 31.8, 30.7, 30.6, 26.7 (Z isomer), 26.1, 26.0 (Z isomer), 19.2, 19.1, 14.2, 13.7, 13.6 ppm.

    [0063] GCMS-EI m/z (%): 310 (M+, 1), 236 (7), 208 (6), 179 (11), 162 (100), 147 (8), 134 (50), 120 (11), 107 (22), 99 (13), 93 (12), 81 (13), 67 (5), 57 (27), 54 (26), 41 (39).

    [0064] EI-HRMS calcd for C.sub.18H.sub.30O.sub.4 [M]+: 310.21386; found: 310.21401.

    Example 7

    Effects of Ligands

    [0065] Examples 8-35 were conducted to determine the effects of ligands used during alkoxycarboxylation of the -lactone 1. FIG. 5 shows the reaction scheme used in determining the effects of the ligands, while FIGS. 6A-6C show the various ligands tested. Essentially, methyl alcohol was the primary alcohol used in all of the experiments in an effort to synthesize the dimethyl ester of formula 2. A summary of the yields and E/Z stereoisomer ratio of the diester products of formula 2 obtained for each ligand is shown in Table 4, below. The experimental procedure for each ligand is described in Examples 8-35.

    TABLE-US-00004 TABLE 4 Effects of Ligands Reaction Yield 2 E/Z Example Pd (mol %) Ligand (mol %) time (h) (%) ratio 8 PdCl.sub.2 (1.0) none 5 29 4.2 9 PdCl.sub.2 (1.0) none 20 42 4.2 10 PdCl.sub.2 (1.0) L1 (4.0 mol %) 5 17 4.0 11 PdCl.sub.2 (1.0) L1 (4.0 mol %) 20 20 3.6 12 PdCl.sub.2 (1.0) L2 (4.0 mol %) 5 39 4.2 13 PdCl.sub.2 (1.0) L3 (2.0 mol %) 5 trace 14 PdCl.sub.2 (1.0) L4 (2.0 mol %) 5 13 4.4 15 PdCl.sub.2 (1.0) L5 (2.0 mol %) 5 3 3.7 16 PdCl.sub.2 (1.0) L5 (2.0 mol %) 20 19 3.7 17 PdCl.sub.2 (1.0) L6 (2.0 mol %) 5 56 3.4 18 PdCl.sub.2 (1.0) L6 (2.0 mol %) 20 10 0.8 19 PdCl.sub.2 (1.0) L7 (2.0 mol %) 5 75 3.8 20 PdCl.sub.2 (1.0) L8 (2.0 mol %) 5 16 2.0 21 PdCl.sub.2 (1.0) L9 (2.0 mol %) 5 44 4.1 22 PdCl.sub.2 (1.0) L10 (2.0 mol %) 5 32 4.1 23 PdCl.sub.2 (1.0) L11 (2.0 mol %) 5 83 3.8 24 PdCl.sub.2 (1.0) L11 (2.0 mol %) 20 85 3.7 25 PdCl.sub.2 (1.0) L12 (2.0 mol %) 5 8 4.4 26 PdCl.sub.2 (1.0) L13 (2.0 mol %) 5 78 3.2 27 PdCl.sub.2 (1.0) L14 (2.0 mol %) 5 1 28 PdCl.sub.2 (1.0) L15 (2.0 mol %) 5 0 29 PdCl.sub.2 (1.0) L16 (2.0 mol %) 5 2 30 PdCl.sub.2 (1.0) L17 (2.0 mol %) 5 9 1.3 31 PdCl.sub.2 (1.0) L17 (2.0 mol %) 20 2 0.8 32 PdCl.sub.2 (1.0) L18 (4.0 mol %) 20 3.5 33 PdCl.sub.2 (1.0) L19 (2.0 mol %) 5 3.8 4.4 34 PdCl.sub.2 (1.0) L20 (2.0 mol %) 5 35 PdCl.sub.2 (1.0) L21 (2.0 mol %) 5

    Example 8

    No Ligand5 hr Reaction Time

    [0066] A 4 mL vial was charged with PdCl.sub.2 (1.7 mg, 1 mol %), -lactone 1 (152 mg, 1.0 mmol) and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. Toluene (2.0 mL) and 0.2 M PTSA.H.sub.2O solution in MeOH (0.25 mL, 5 mol %), were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was performed for 5 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 9

    No Ligand20 hr Reaction Time

    [0067] A 4 mL vial was charged with PdCl.sub.2 (1.7 mg, 1 mol %), -lactone 1 (152 mg, 1.0 mmol) and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. Toluene (2.0 mL) and 0.2 M PTSA. H.sub.2O solution in MeOH (0.25 mL, 5 mol %), were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4560 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was performed for 20 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 10

    Ligand L1-5 hr Reaction Time

    [0068] A 4 mL vial was charged with PdCl.sub.2 (1.7 mg, 1 mol %), L1 (11.0 mg, 4 mol %), -lactone 1 (152 mg, 1.0 mmol) and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. Toluene (2.0 mL) and 0.2 M PTSA.H.sub.2O solution in MeOH (0.25 mL, 5 mol %), were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was performed for 5 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 11

    Ligand L120 hr Reaction Time

    [0069] A 4 mL vial was charged with PdCl.sub.2 (1.7 mg, 1 mol %), L1 (10.8 mg, 4 mol %), -lactone 1 (152 mg, 1.0 mmol) and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. Toluene (2.0 mL) and 0.2 M PTSA.H.sub.2O solution in MeOH (0.25 mL, 5 mol %), were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was performed for 20 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 12

    Ligand L25 hr Reaction Time

    [0070] A 4 mL vial was charged with PdCl.sub.2 (1.7 mg, 1 mol %), L2 (14.1 mg, 4 mol %), -lactone 1 (152 mg, 1.0 mmol) and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. Toluene (2.0 mL) and 0.2 M PTSA.H.sub.2O solution in MeOH (0.25 mL, 5 mol %), were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was performed for 5 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 13

    Ligand L35 hr Reaction Time

    [0071] A 4 mL vial was charged with PdCl.sub.2 (1.7 mg, 1 mol %), L3 (8.0 mg, 2 mol %), -lactone 1 (152 mg, 1.0 mmol) and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. Toluene (2.0 mL) and 0.2 M PTSA.H.sub.2O solution in MeOH (0.25 mL, 5 mol %), were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was performed for 5 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 14

    Ligand L45 hr Reaction Time

    [0072] A 4 mL vial was charged with PdCl.sub.2 (1.7 mg, 1.0 mol %), L4 (8.6 mg, 2 mol %), -lactone 1 (152 mg, 1.0 mmol) and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. Toluene (2.0 mL) and 0.2 M PTSA.H.sub.2O solution in MeOH (0.25 mL, 5 mol %), were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was performed for 5 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 15

    Ligand L55 hr Reaction Time

    [0073] A 4 mL vial was charged with PdCl.sub.2 (1.7 mg, 1 mol %), L5 (10.6 mg, 2 mol %), lactone 1 (152 mg, 1.0 mmol) and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. Toluene (2.0 mL) and 0.2 M PTSA.H.sub.2O solution in MeOH (0.25 mL, 5 mol %), were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was performed for 5 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 16

    Ligand L520 hr Reaction Time

    [0074] A 4 mL vial was charged with PdCl.sub.2 (1.7 mg, 1 mol %), L5 (10.6 mg, 2 mol %), -lactone 1 (152 mg, 1.0 mmol) and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. Toluene (2.0 mL) and 0.2 M PTSA.H.sub.2O solution in MeOH (0.25 mL, 5 mol %), were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was performed for 20 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 17

    Ligand L65 hr Reaction Time

    [0075] A 4 mL vial was charged with PdCl.sub.2 (1.7 mg, 1 mol %), L6 (11.7 mg, 2 mol %), -lactone 1 (152 mg, 1.0 mmol) and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. Toluene (2.0 mL) and 0.2 M PTSA.H.sub.2O solution in MeOH (0.25 mL, 5 mol %), were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was performed for 5 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 18

    Ligand L620 hr Reaction Time

    [0076] A 4 mL vial was charged with PdCl.sub.2 (1.7 mg, 1 mol %), L6 (11.7 mg, 2 mol %), -lactone 1 (152 mg, 1.0 mmol) and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. Toluene (2.0 mL) and 0.2 M PTSA.H.sub.2O solution in MeOH (0.25 mL, 5 mol %), were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was performed for 20 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 19

    Ligand L75 hr Reaction Time

    [0077] A 4 mL vial was charged with PdCl.sub.2 (1.7 mg, 1 mol %), L7 (24.6 mg, 2 mol %), -lactone 1 (152 mg, 1.0 mmol) and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. Toluene (2.0 mL) and 0.2 M PTSA.H.sub.2O solution in MeOH (0.25 mL, 5 mol %), were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was performed for 5 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 20

    Ligand L85 hr Reaction Time

    [0078] A 4 mL vial was charged with PdCl.sub.2 (1.7 mg, 1 mol %), L8 (14.2 mg, 2 mol %), -lactone 1 (152 mg, 1.0 mmol) and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. Toluene (2.0 mL) and 0.2 M PTSA.H.sub.2O solution in MeOH (0.25 mL, 5 mol %), were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was performed for 5 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 21

    Ligand L95 hr Reaction Time

    [0079] A 4 mL vial was charged with PdCl.sub.2 (1.7 mg, 1 mol %), L9 (11.2 mg, 2 mol %), -lactone 1 (152 mg, 1.0 mmol) and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. Toluene (2.0 mL) and 0.2 M PTSA.H.sub.2O solution in MeOH (0.25 mL, 5 mol %), were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was performed for 5 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 22

    Ligand L105 hr Reaction Time

    [0080] A 4 mL vial was charged with PdCl.sub.2 (1.7 mg, 1 mol %), L10 (12.9 mg, 2 mol %), -lactone 1 (152 mg, 1.0 mmol) and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. Toluene (2.0 mL) and 0.2 M PTSA.H.sub.2O solution in MeOH (0.25 mL, 5 mol %), were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was performed for 5 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 23

    Ligand L115 hr Reaction Time

    [0081] A 4 mL vial was charged with PdCl.sub.2 (1.7 mg, 1 mol %), L11 (23.5 mg, 2 mol %), -lactone 1 (152 mg, 1.0 mmol) and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. Toluene (2.0 mL) and 0.2 M PTSA.H.sub.2O solution in MeOH (0.25 mL, 5 mol %), were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was performed for 5 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 24

    Ligand L1120 hr Reaction Time

    [0082] A 4 mL vial was charged with PdCl.sub.2 (1.7 mg, 1 mol %), L11 (23.5 mg, 2 mol %), -lactone 1 (152 mg, 1.0 mmol) and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. Toluene (2.0 mL) and 0.2 M PTSA.H.sub.2O solution in MeOH (0.25 mL, 5 mol %), were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was performed for 20 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 25

    Ligand L125 hr Reaction Time

    [0083] A 4 mL vial was charged with PdCl.sub.2 (1.7 mg, 1 mol %), L12 (12.9 mg, 2 mol %), -lactone 1 (152 mg, 1.0 mmol) and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. Toluene (2.0 mL) and 0.2 M PTSA.H.sub.2O solution in MeOH (0.25 mL, 5 mol %), were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was performed for 5 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 26

    Ligand L135 hr Reaction Time

    [0084] A 4 mL vial was charged with PdCl.sub.2 (1.7 mg, 1 mol %), L13 (15.6 mg, 2 mol %), -lactone 1 (152 mg, 1.0 mmol) and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. Toluene (2.0 mL) and 0.2 M PTSA.H.sub.2O solution in MeOH (0.25 mL, 5 mol %), were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was performed for 5 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 27

    Ligand L145 hr Reaction Time

    [0085] A 4 mL vial was charged with PdCl.sub.2 (1.7 mg, 1 mol %), L14 (17.2 mg, 2 mol %), -lactone 1 (152 mg, 1.0 mmol) and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. Toluene (2.0 mL) and 0.2 M PTSA.H.sub.2O solution in MeOH (0.25 mL, 5 mol %), were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was performed for 5 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 28

    Ligand L155 hr Reaction Time

    [0086] A 4 mL vial was charged with PdCl.sub.2 (1.7 mg, 1 mol %), L15 (10.7 mg, 2 mol %), -lactone 1 (152 mg, 1.0 mmol) and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. Toluene (2.0 mL) and 0.2 M PTSA.H.sub.2O solution in MeOH (0.25 mL, 5 mol %), were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was performed for 5 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 29

    Ligand L165 hr Reaction Time

    [0087] A 4 mL vial was charged with PdCl.sub.2 (1.7 mg, 1 mol %), L16 (10.4 mg, 2 mol %), -lactone 1 (152 mg, 1.0 mmol) and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. Toluene (2.0 mL) and 0.2 M PTSA.H.sub.2O solution in MeOH (0.25 mL, 5 mol %), were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was performed for 5 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 30

    Ligand L175 hr Reaction Time

    [0088] A 4 mL vial was charged with PdCl.sub.2 (1.7 mg, 1 mol %), L17 (7.8 mg, 2 mol %), -lactone 1 (152 mg, 1.0 mmol) and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. Toluene (2.0 mL) and 0.2 M PTSA.H.sub.2O solution in MeOH (0.25 mL, 5 mol %), were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was performed for 5 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 31

    Ligand L1720 hr Reaction Time

    [0089] A 4 mL vial was charged with PdCl.sub.2 (1.7 mg, 1 mol %), L17 (7.8 mg, 2 mol %), -lactone 1 (152 mg, 1.0 mmol) and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. Toluene (2.0 mL) and 0.2 M PTSA.H.sub.2O solution in MeOH (0.25 mL, 5 mol %), were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was performed for 20 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 32

    Ligand L1820 hr Reaction Time

    [0090] A 4 mL vial was charged with PdCl.sub.2 (1.7 mg, 1 mol %), L18 (11.0 mg, 4 mol %), -lactone 1 (152 mg, 1.0 mmol) and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. Toluene (2.0 mL) and 0.2 M PTSA.H.sub.2O solution in MeOH (0.25 mL, 5 mol %), were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was performed for 20 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 33

    Ligand L195 hr Reaction Time

    [0091] A 4 mL vial was charged with PdCl.sub.2 (1.7 mg, 1 mol %), L19 (11.1 mg, 2 mol %), -lactone 1 (152 mg, 1.0 mmol) and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. Toluene (2.0 mL) and 0.2 M PTSA.H.sub.2O solution in MeOH (0.25 mL, 5 mol %), were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was performed for 5 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 34

    Ligand L205 hr Reaction Time

    [0092] A 4 mL vial was charged with PdCl.sub.2 (1.7 mg, 1 mol %), L20 (18.8 mg, 2 mol %), -lactone 1 (152 mg, 1.0 mmol) and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. Toluene (2.0 mL) and 0.2 M PTSA.H.sub.2O solution in MeOH (0.25 mL, 5 mol %), were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was performed for 5 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 35

    Ligand L215 hr Reaction Time

    [0093] A 4 mL vial was charged with PdCl.sub.2 (1.7 mg, 1 mol %), L21 (11.6 mg, 2 mol %), -lactone 1 (152 mg, 1.0 mmol) and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. Toluene (2.0 mL) and 0.2 M PTSA.H.sub.2O solution in MeOH (0.25 mL, 5 mol %), were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was performed for 5 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 36

    Effects of Acids

    [0094] Examples 37-39 were conducted to determine the effects of the acid promoter used during synthesis. FIG. 7 shows the reaction scheme used in determining the effects of the acid. A summary of the yields and E/Z stereoisomer ratio of the diester products of formula 2 obtained for each ligand is shown in Table 5, below. The experimental procedure for each ligand is described in Examples 37-39.

    TABLE-US-00005 TABLE 5 Effects of Acid Example Acid (mol %) Yield 2 (%) E/Z ratio 37 CH.sub.3SO.sub.3H (5.0) 84 3.9 38 HCl (5.0) 33 3.7 39 H.sub.2SO.sub.4 (5.0) 89 4.1

    Example 37

    Methanesulfonic Acid

    [0095] A 4 mL vial was charged with PdCl.sub.2 (1.7 mg, 1 mol %), -lactone 1 (152 mg, 1.0 mmol), L11 (23.5 mg, 2 mol %) and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. Toluene (2.0 mL) and 0.2 M methanesulfonic acid (CH.sub.3SO.sub.3H) solution in MeOH (0.25 mL, 5 mol %), were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was performed for 5 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 38

    Hydrochloric Acid

    [0096] A 4 mL vial was charged with PdCl.sub.2 (1.7 mg, 1 mol %), -lactone 1 (152 mg, 1.0 mmol), L11 (23.5 mg, 2 mol %) and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. Toluene (2.0 mL), HCl (2M in diethylether) (0.025 mL, 5.0 mol %) and MeOH (0.25 mL), were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was performed for 5 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 39

    Sulfuric Acid

    [0097] A 4 mL vial was charged with PdCl.sub.2 (1.7 mg, 1 mol %), -lactone 1 (152 mg, 1.0 mmol), L11 (23.5 mg, 2 mol %) and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. Toluene (2.0 mL) and 0.2 M H.sub.2SO.sub.4 solution in MeOH (0.25 mL, 5 mol %), were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was performed for 5 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 40

    Effect of Solvent

    [0098] Examples 41-43 were conducted to determine the effects of solvents used during synthesis on the yield of compound 2. FIG. 8 shows the scheme used in determining the effect of the solvent. The effects of the various solvents are summarized in Table 6, shown below.

    TABLE-US-00006 TABLE 6 Effect of Solvent Example Solvent Yield 2 (%) E/Z ratio 41 CH.sub.3CN 37 4.0 42 MeOH 45 3.8 43 THF 39 4.2

    Example 41

    Acetonitrile

    [0099] A 4 mL vial was charged with PdCl.sub.2 (1.7 mg, 1 mol %), -lactone 1 (152 mg, 1.0 mmol), L11 (23.5 mg, 2 mol %) and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. CH.sub.3CN (2.0 mL) and 0.2 M H.sub.2SO.sub.4 solution in MeOH (0.25 mL, 5 mol %), were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was performed for 5 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 42

    Methyl Alcohol

    [0100] A 4 mL vial was charged with PdCl.sub.2 (1.7 mg, 1 mol %), -lactone 1 (152 mg, 1.0 mmol), L11 (23.5 mg, 2 mol %) and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. MeOH (2.0 mL) and 0.2 M H.sub.2SO.sub.4 solution in MeOH (0.25 mL, 5 mol %), were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was performed for 5 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 43

    Tetrahydrofuran

    [0101] A 4 mL vial was charged with PdCl.sub.2 (1.7 mg, 1 mol %), -lactone 1 (152 mg, 1.0 mmol), L11 (23.5 mg, 2 mol %) and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. THF (2.0 mL) and 0.2 M H.sub.2SO.sub.4 solution in MeOH (0.25 mL, 5 mol %), were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was performed for 5 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 44

    Effect of Palladium Precursor

    [0102] Examples 45-47 were conducted to determine the effects of the palladium precursor used during synthesis on the yield of compound 2. FIG. 9 shows the scheme used in determining the effects of the palladium precursor. The effects of the various precursors are summarized in Table 7, shown below.

    TABLE-US-00007 TABLE 7 Effect of Palladium Precursor Example Pd Precursor (mol %) Yield 2 (%) E/Z ratio 45 PdCl.sub.2(CH.sub.3CN).sub.2 (1.0) 88 4.0 46 Pd(dba).sub.2 (1.0) 16 3.8 47 Pd(OAc).sub.2 (1.0) 19 3.7

    Example 45

    Bis(Acetonitrile)Dichloropalladium(II)

    [0103] A 4 mL vial was charged with PdCl.sub.2(CH.sub.3CN).sub.2 (2.6 mg, 1 mol %), -lactone 1 (152 mg, 1.0 mmol), L11 (23.5 mg, 2 mol %) and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. Toluene (2.0 mL) and 0.2 M H.sub.2SO.sub.4 solution in MeOH (0.25 mL, 5 mol %), were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was performed for 5 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 46

    Bis(Dibenzylideneacetone)Palladium(0)

    [0104] A 4 mL vial was charged with Pd(dba).sub.2 (5.7 mg, 1 mol %), -lactone 1 (152 mg, 1.0 mmol), L11 (23.5 mg, 2 mol %) and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. Toluene (2.0 mL) and 0.2 M H.sub.2SO.sub.4 solution in MeOH (0.25 mL, 5 mol %), were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was performed for 5 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 47

    Palladium Acetate

    [0105] A 4 mL vial was charged with Pd(OAc).sub.2 (2.3 mg, 1 mol %), 3-lactone 1 (152 mg, 1.0 mmol), L11 (23.5 mg, 2 mol %) and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. Toluene (2.0 mL) and 0.2 M H.sub.2SO.sub.4 solution in MeOH (0.25 mL, 5 mol %), were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was performed for 5 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 48

    Effect of Acid and Methanol Amounts

    [0106] Examples 49-56 were conducted to determine the effect of the acid and methanol amounts used during synthesis on the yield of compound 2. FIG. 10 shows the scheme used in determining the effects of the acid and methanol amounts. The effects are summarized in Table 8, shown below.

    TABLE-US-00008 TABLE 8 Effect of Acid and Methanol Amounts Yield 2 Example mL MeOH Acid (mol %) (%) E/Z ratio 49 0.25 (6.0 eq) PTSAH.sub.2O (1.0) 58 4.0 50 0.25 (6.0 eq) PTSAH.sub.2O (10.0) 89 4.1 51 0.08 (2.0 eq) PTSAH.sub.2O (15.0) 55 2.6 52 0.12 (3.0 eq) PTSAH.sub.2O (15.0) 81 3.6 53 0.25 (6.0 eq) PTSAH.sub.2O (15.0) 90 4.0 54 0.25 (6.0 eq) PTSAH.sub.2O (21.0) 92 4.1 55 0.25 (6.0 eq) H.sub.2SO.sub.4 (7.5) 91 4.1 56 0.50 (12.0 eq) H.sub.2SO.sub.4 (5.0) 91 4.2

    Example 49

    MeOH (6.0 Eq.)/PTSA 1.0 Mol. %

    [0107] A 4 mL vial was charged with PdCl.sub.2 (1.7 mg, 1 mol %), -lactone 1 (152 mg, 1.0 mmol), L11 (23.5 mg, 2 mol %) and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. Toluene (2.0 mL), 0.2 M PTSA.H.sub.2O solution in MeOH (0.050 mL, 1 mol %) and MeOH (0.20 mL) were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was performed for 5 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 50

    MeOH 6.0 Eq./PTSA 10.0 Mol. %

    [0108] A 4 mL vial was charged with PdCl.sub.2 (1.7 mg, 1 mol %), -lactone 1 (152 mg, 1.0 mmol), L11 (23.5 mg, 2 mol %), PTSA.H.sub.2O (19.0 mg, 10 mol %) and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. Toluene (2.0 mL), and MeOH (0.25 mL) were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was performed for 5 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 51

    MeOH 2.0 Eq./PTSA 15 Mol. %

    [0109] A 4 mL vial was charged with PdCl.sub.2 (1.7 mg, 1 mol %), -lactone 1 (152 mg, 1.0 mmol), L11 (23.5 mg, 2 mol %), PTSA.H.sub.2O (28.4 mg, 15 mol %) and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. Toluene (2.0 mL), and MeOH (0.08 mL) were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was performed for 5 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 52

    MeOH 3.0 Eq./PTSA 15 Mol. %

    [0110] A 4 mL vial was charged with PdCl.sub.2 (1.7 mg, 1 mol %), -lactone 1 (152 mg, 1.0 mmol), L11 (23.5 mg, 2 mol %), PTSA.H.sub.2O (28.4 mg, 15 mol %) and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. Toluene (2.0 mL), and MeOH (0.12 mL) were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was performed for 5 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 53

    MeOH 6.0 Eq,/PTSA 15 Mol. %

    [0111] A 4 mL vial was charged with PdCl.sub.2 (1.7 mg, 1 mol %), -lactone 1 (152 mg, 1.0 mmol), L11 (23.5 mg, 2 mol %), PTSA.H.sub.2O (28.4 mg, 15 mol %) and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. Toluene (2.0 mL), and MeOH (0.25 mL) were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was performed for 5 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 54

    MeOH 6.0 Eq./PTSA 21 Mol. %

    [0112] A 4 mL vial was charged with PdCl.sub.2 (1.7 mg, 1 mol %), -lactone 1 (152 mg, 1.0 mmol), L11 (23.5 mg, 2 mol %), PTSA.H.sub.2O (40.0 mg, 21 mol %) and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. Toluene (2.0 mL) and MeOH (0.25 mL) were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was performed for 5 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 55

    MeOH 6.0 Eq./H.SUB.2.SO.SUB.4 .7.5 Mol. %

    [0113] A 4 mL vial was charged with PdCl.sub.2 (1.7 mg, 1 mol %), -lactone 1 (152 mg, 1.0 mmol), L11 (23.5 mg, 2 mol %) and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. Toluene (2.0 mL) and 0.3 M H.sub.2SO.sub.4 solution in MeOH (0.250 mL, 7.5 mol %) were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was performed for 5 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 56

    MeOH 12.0 Eq./H.SUB.2.SO.SUB.4 .5.0 Mol. %

    [0114] A 4 mL vial was charged with PdCl.sub.2 (1.7 mg, 1 mol %), -lactone 1 (152 mg, 1.0 mmol), L11 (23.5 mg, 2 mol %) and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. Toluene (2.0 mL), 0.2 M H.sub.2SO.sub.4 solution in MeOH (0.250 mL, 5 mol %) and MeOH (0.25 35 mL) were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was performed for 5 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 57

    Effects of Pressure

    [0115] Examples 58-61 were conducted to determine the effects of pressure used during synthesis of compound 2. FIG. 11 shows the scheme used in determining the effects of pressure. The effects of pressure are summarized in Table 9 shown below.

    TABLE-US-00009 TABLE 9 Effect of Pressure Example Acid (mol %) P.sub.CO (bar) Yield 2 (%) E/Z ratio 58 H.sub.2SO.sub.4 (5 mol %) 50 89 4.0 59 H.sub.2SO.sub.4 (5 mol %) 40 89 4.0 60 H.sub.2SO.sub.4 (5 mol %) 30 89 4.0 61 H.sub.2SO.sub.4 (5 mol %) 20 87 3.9

    Example 58

    50 Bar Pressure

    [0116] A 4 mL vial was charged -lactone 1 (152 mg, 1.0 mmol), and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. A solution of PdCl.sub.2 (0.85 mg, 0.5 mol %) and L11 (11.9 mg, 1 mol %) in toluene (2.0 mL) and 0.2 M H.sub.2SO.sub.4 solution in MeOH (0.25 mL, 5 mol %), were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 50 bar at room temperature. The reaction was performed for 3 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 59

    40 Bar Pressure

    [0117] A 4 mL vial was charged -lactone 1 (152 mg, 1.0 mmol), and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. A solution of PdCl.sub.2 (0.85 mg, 0.5 mol %) and L11 (11.9 mg, 1 mol %) in toluene (2.0 mL) and 0.2 M H.sub.2SO.sub.4 solution in MeOH (0.25 mL, 5 mol %), were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was performed for 3 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 60

    30 Bar Pressure

    [0118] A 4 mL vial was charged -lactone 1 (152 mg, 1.0 mmol), and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. A solution of PdCl.sub.2 (0.85 mg, 0.5 mol %) and L11 (11.9 mg, 1 mol %) in toluene (2.0 mL) and 0.2 M H.sub.2SO.sub.4 solution in MeOH (0.25 mL, 5 mol %), were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 30 bar at room temperature. The reaction was performed for 3 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 61

    20 Bar Pressure

    [0119] A 4 mL vial was charged -lactone 1 (152 mg, 1.0 mmol), and a magnetic stirring bar. The 40 vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. A solution of PdCl.sub.2 (0.85 mg, 0.5 mol %) and L11 (11.9 mg, 1 mol %) in toluene (2.0 mL) and 0.2 M H.sub.2SO.sub.4 solution in MeOH (0.25 mL, 5 mol %), were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 20 bar at room temperature. The reaction was performed for 3 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 62

    Effect of Temperature

    [0120] Examples 63-65 were conducted to determine the effect of temperature used during synthesis on yield of compound 2. FIG. 12 shows the scheme used in determining the effect of temperature. The effect of temperature is summarized in Table 10, shown below.

    TABLE-US-00010 TABLE 10 Effect of Temperature Example Acid (mol %) T ( C.) Yield 2 (%) E/Z ratio 63 H.sub.2SO.sub.4 (5 mol %) 130 86 4.0 64 H.sub.2SO.sub.4 (5 mol %) 120 89 4.0 65 H.sub.2SO.sub.4 (5 mol %) 110 87 4.1

    Example 63

    Temp 130 C.

    [0121] A 4 mL vial was charged -lactone 1 (152 mg, 1.0 mmol), and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. A solution of PdCl.sub.2 (0.85 mg, 0.5 mol %) and L11 (11.9 mg, 1 mol %) in toluene (2.0 mL) and 0.2 M H.sub.2SO.sub.4 solution in MeOH (0.25 mL, 5 mol %), were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was performed for 3 h at 130 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 64

    Temp 120 C.

    [0122] A 4 mL vial was charged -lactone 1 (152 mg, 1.0 mmol), and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. A solution of PdCl.sub.2 (0.85 mg, 0.5 mol %) and L11 (11.9 mg, 1 mol %) in toluene (2.0 mL) and 0.2 M H.sub.2SO.sub.4 solution in MeOH (0.25 mL, 5 mol %), were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was performed for 3 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 65

    Temp 110 C.

    [0123] A 4 mL vial was charged -lactone 1 (152 mg, 1.0 mmol), and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. A solution of PdCl.sub.2 (0.85 mg, 0.5 mol %) and L11 (11.9 mg, 1 mol %) in toluene (2.0 mL) and 0.2 M H.sub.2SO.sub.4 solution in MeOH (0.25 mL, 5 mol %), were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was performed for 3 h at 110 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 66

    Alcohol Scope

    [0124] Examples 67-73 were conducted to determine the scope of alcohol during synthesis. FIG. 13 shows the scheme used in determining the scope of alcohol. The results are summarized in Table 11, shown below.

    TABLE-US-00011 TABLE 11 Scope of Alcohol Example Alcohol Acid (mol %) Yield 2 (%) E/Z ratio 67 MeOH H.sub.2SO.sub.4 (5 mol %) 90 4.3 (6.0 equiv.) 68 nBuOH H.sub.2SO.sub.4 (5 mol %) 90 3.8 (6.0 equiv.) 69 2-Ethylhexanol H.sub.2SO.sub.4 (5 mol %) 99 4.2 (6.0 equiv.) 70 iPrOH H.sub.2SO.sub.4 (5 mol %) 64 2.3 (6.0 equiv.) 71 tBuOH PTSAH.sub.2O (6.0 equiv.) (10 mol %) 72 PhCH.sub.2OH PTSAH.sub.2O 73 4.5 (6.0 equiv.) (10 mol %) 73 PhOH PTSAH.sub.2O (6.0 equiv.) (10 mol %)

    Example 67

    MeOH (6 Eq.)/H.SUB.2.SO.SUB.4 .(5 Mol %)

    [0125] A 4 mL vial was charged -lactone 1 (152 mg, 1.0 mmol), and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. A solution of PdCl.sub.2 (0.85 mg, 0.5 mol %) and L11 (11.9 mg, 1 mol %) in toluene (2.0 mL) and 0.2 M H.sub.2SO.sub.4 solution in MeOH (0.25 mL, 5 mol %), were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 30 bar at room temperature. The reaction was performed for 5 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. Then hexadecane (0.100 mL) was injected as the internal standard. Yield and selectivity were measured by GC analysis.

    Example 68

    n-Butanol/H.SUB.2.SO.SUB.4 .(5 Mol %)

    [0126] A 4 mL vial was charged -lactone 1 (152 mg, 1.0 mmol), and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. A solution of PdCl.sub.2 (0.85 mg, 0.5 mol %) and L11 (11.9 mg, 1 mol %) in toluene (2.0 mL) and 0.096 M H.sub.2SO.sub.4 solution in n-butanol (0.55 mL, 6 mmol) were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 30 bar at room temperature. The reaction was performed for 5 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. The isomeric ratio was measured by GC analysis. Isolated yield.

    Example 69

    2-Ethylhexanol/H.SUB.2.SO.SUB.4 .(5 Mol %)

    [0127] A 4 mL vial was charged -lactone 1 (152 mg, 1.0 mmol), and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. A solution of PdCl.sub.2 (0.85 mg, 0.5 mol %) and L11 (11.9 mg, 1 mol %) in toluene (2.0 mL) and 0.053 M H.sub.2SO.sub.4 solution in 2-ethylhexanol (0.94 mL, 6 mmol), were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 30 bar at room temperature. The reaction was performed for 5 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. The isomeric ratio was measured by GC analysis. Isolated yield.

    Example 70

    i-Propanol/H.SUB.2.SO.SUB.4 .(5 Mol %)

    [0128] A 4 mL vial was charged -lactone 1 (152 mg, 1.0 mmol), and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. A solution of PdCl.sub.2 (0.85 mg, 0.5 mol %) and L11 (11.9 mg, 1 mol %) in toluene (2.0 mL) and 0.109 M H.sub.2SO.sub.4 solution in i-propanol (0.46 mL, 6 mmol), were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 30 bar at room temperature. The reaction was performed for 5 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. The isomeric ratio was measured by GC analysis. Isolated yield.

    Example 71

    t-Butanol/PTSA (10 Mol %)

    [0129] A 4 mL vial was charged -lactone 1 (152 mg, 1.0 mmol), PTSA.H.sub.2O (19.0 mg, 10 mol %), t-butanol (450 mg, 6 mmol) and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. A solution of PdCl.sub.2 (0.85 mg, 0.5 mol %) and L11 (11.9 mg, 1 mol %) in toluene (2.0 mL) was injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 30 bar at room temperature. The reaction was performed for 5 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. The diester was not detected by GC-MS analysis.

    Example 72

    Benzyl Alcohol/PTSA (10 Mol %)

    [0130] A 4 mL vial was charged -lactone 1 (152 mg, 1.0 mmol), PTSA.H.sub.2O (19.0 mg, 10 mol %) and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. A solution of PdCl.sub.2 (0.85 mg, 0.5 mol %) and L11 (11.9 mg, 1 mol %) in toluene (2.0 mL) and benzyl alcohol (0.62 mL, 6 mmol), were injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 30 bar at room temperature. The reaction was performed for 5 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. The isomeric ratio was measured by GC analysis. Isolated yield.

    Example 73

    Phenol/PTSA (10 Mol %)

    [0131] A 4 mL vial was charged -lactone 1 (152 mg, 1.0 mmol), PTSA.H.sub.2O (19.0 mg, 10 mol %), phenol (565 mg, 6 mmol) and a magnetic stirring bar. The vial was then sealed with Septa (PTFE-faced styrene-butadiene rubber) and phenolic cap. The vial was then connected to the atmosphere with a needle. The vial was evacuated and refilled with argon three times. A solution of PdCl.sub.2 (0.85 mg, 0.5 mol %) and L11 (11.9 mg, 1 mol %) in toluene (2.0 mL) was injected into the vial by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 mL) of the 4760 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 30 bar at room temperature. The reaction was performed for 5 h at 120 C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released. The diester was not detected by GC-MS analysis.

    [0132] The unsaturated esters obtained by the alkoxycarbonylation of 1 are valuable platform chemicals themselves. However, the corresponding saturated esters and the resulting diols are also of interest for applications. In order to transform 2 into saturated esters or diols, the metal-catalyzed alkoxycarbonylation of a lactone was extended by performing catalytic hydrogenations.

    [0133] At first, commercial Pd/C (10 wt %) was used as the catalyst to hydrogenate the unsaturated diester 2a. See FIG. 14. Mild reaction conditions (10 bar H.sub.2, 60 C.), previously reported by Behr and coworkers for the reduction of lactone 1 to 3,6-diethyltetrahydro-2H-pyran-2-one were used. We noticed a marked solvent effect on the chemoselectivity of the hydrogenation. When the reaction was performed in toluene, reduction of the di-substituted double bond was attained within 3 hours. However, the conjugated tri-substituted double bond was not reduced, even after 16 h. Complete reduction of the olefinic bonds of 2a to yield 4 was instead accomplished in 2.5 h using THF as the solvent (see FIG. 15). The latter diester 4 is of potential industrial interest for plasticizer applications and as a co-monomer in combination with diamines and diols to yield, respectively, polyamides and polyesters. On the other hand, the presence of a single unsaturation makes 3 comparable to 1,3-unsaturated esters, e.g., acrylic and tiglic acid derivatives, which are of interest for the preparation of different functional materials.

    Example 74

    Synthesis of Dimethyl 2-Ethyloctanedioate (Compound 4)

    [0134] Pd/C 10 wt % (3.1 mg), compound 2a (1.4 mmol) and a magnetic stirring bar were added to a 4 mL vial. The vial was then sealed, connected to the atmosphere with a needle, and evacuated and refilled with argon three times. THF (3 mL) was added, and the vial placed inside a 300 mL stainless steel Parr autoclave. The autoclave was flushed three times with nitrogen, pressurized with hydrogen to 10 bar, and then heated to 60 C. for 2.5 h. The autoclave was cooled with an ice bath and vented. The reaction mixture was filtered through Celite, and the solvent evaporated, affording pure 4 as a colorless liquid in >99% yield.): .sup.1H NMR (300 MHz, CDCl.sub.3) 3.61 (s, 3H), 3.60 (s, 3H), 2.32-2.14 (m, 3H), 1.49 (m, 6H), 1.32-1.12 (m, 4H), 0.82 ppm (t, J=7.4 Hz, 3H). .sup.13C NMR (75 MHz, CDCl.sub.3) 176.7, 174.1, 51.5, 51.3, 47.2, 34.0, 31.9, 29.1, 27.1, 25.5, 24.8, 11.8 ppm. GCMS-EI m/z (%)=199 (8), 171 (25), 166 (34), 157 (13), 138 (29), 129 (22), 114 (11), 102 (97), 97 (45), 87 (100), 69 (56), 59 (93), 55 (97), 41 (57). ESI-HRMS calcd for C.sub.12H.sub.220.sub.4Na [M+Na]+: 253.14103; found: 253.14109.

    [0135] To further illustrate the versatility of 2 as a building block for polymers, we studied its hydrogenation to diol 5 (see FIGS. 16-17). The synthesis of 5 can be performed by the reduction of 4 using LiAlH.sub.4 as the stoichiometric reagent, a classical method used in laboratory organic synthesis. However, when we performed this reaction, we found that the separation and purification of 5 from byproducts was difficult. Such a methodology is clearly not environmentally acceptable and not applicable to bulk scale industrial production. Thus, catalytic hydrogenation was investigated.

    [0136] Ester and carboxylic acid moieties are challenging functional groups for hydrogenation reactions. In industrial processes, their hydrogenation is generally performed over heterogeneous catalysts at high pressures and temperatures. However, recently homogenously catalyzed hydrogenation of carboxylic acid derivatives has experienced significant developments.

    [0137] Hence, we applied two different commercially available ruthenium based catalysts to the reduction of 2a to 5, including a Noyori-type ruthenium catalyst first reported by Saudan et al. for the hydrogenation of esters (catalyst c1, FIG. 17) and the tetrahydro-borato form of the ruthenium PNP pincer complex named Ru-MACHO (catalyst c2, FIG. 17) discovered by Kuriyama and coworkers at Takasago company. In both cases, reaction conditions commonly used for these catalytic systems were employed (Table 12, below, entries 1 and 2). Unfortunately, even after 22 h only traces of diol were present using c1 as the catalyst, and just 8% yield was obtained using c2. Promising results were instead obtained using ruthenium complexes of 1,1,1-tris-(diphenylphosphinomethyl)ethane (Triphos). Here, we started our investigation using both c4 (ruthenium acetylacetonate/Triphos) in combination with MSA in methanol (entry 3, Table 12) and c3 in THF in the absence of any additive (entry 4, Table 12). The first system yielded 35% of diol 5, while the latter afforded mainly a mixture of the esters 3 and 4. Encouraged by the result obtained with MSA, we tested sodium methoxide and bis(trifluoromethane)sulfonimide (HNTf.sub.2) as additives. The use of HNTf.sub.2 (10 mol %) afforded 69% yield of 5 (entry 5, Table 12). Finally, the desired full reduction of 2a to diol 5 was obtained under relatively mild conditions in 91% yield (80% isolated) upon reduction of the amount of HNTf.sub.2 to 5 mol % and addition of 5 mol % of metallic zinc (entry 7, Table 12).

    TABLE-US-00012 TABLE 12 Hydrogenation of diester 2a to diol 5 Entry Catalyst Solvent Additive (mol %) CO (bar) T ( C.) t (h) 5 Yield (%) 1 c1 THF MeONa (10) 50 120 22 traces 2 c2 THF 50 120 22 8 3 c3 THF 70 150 22 2 4 c4 MeOH MSA (10) 70 150 22 35 5 c4 MeOH HNTf.sub.2 (10) 70 150 22 69 6 c4 MeOH MSA(5)/Zn(5) 70 150 24 42 7 c4 MeOH HNTf.sub.2(5)/Zn(5) 70 150 24 91 8 c4 MeOH MeONa 70 150 22 17 9 c4 dioxane HNTf.sub.2(5) 70 150 22 24 Reaction conditions: 2a (0.5 mmol), metal complex (0.01 mmol), ligand when added (0.02 mmol), solvent (2 mL). Conversion of 2a was complete in all cases. Yields were determined by GC analysis using hexadecane as the internal standard.

    Example 75

    Synthesis of 2-Ethyloctane-1,8-Diol, Compound 5

    [0138] [Ru(acac).sub.3] (4.0 mg, 0.01 mmol), Triphos (12.5 mg, 0.02 mmol) and zinc (1.6 mg, 2.510.sup.2 mmol) were weighed in a 4 mL vial in air. The vial was then sealed, connected to the atmosphere with a needle and evacuated and refilled with argon three times. Compound 2a (0.5 mmol) and 2 mL of a stock solution of HNTf.sub.2 (7.0 mg, 2.510.sup.2 mmol) in methanol were added. The vial was placed inside a 300 mL stainless steel Parr autoclave, and the autoclave was flushed three times with nitrogen, pressurized with hydrogen and heated. After 24 h, the autoclave was cooled with ice water and vented. The crude mixture was analyzed by gas chromatography. The product was purified by column chromatography on silica gel (gradient elution from CH.sub.2Cl.sub.2 to CH.sub.2Cl.sub.2/MeOH 9:1). .sup.1H NMR (300 MHz, CDCl.sub.3) 3.63 (t, J=6.6 Hz, 2H), 3.53 (d, J=5.0 Hz, 2H), 2.42 (br s, 2H), 1.70-1.47 (m, 2H), 1.44-1.15 (m, 11H), 0.88 ppm (t, J=7.3 Hz, 3H). .sup.13C NMR (75 MHz, CDCl.sub.3) 65.0, 62.7, 41.9, 32.7, 30.3, 29.8, 26.8, 25.7, 23.3, 11.1. GCMS-EI m/z (%)=172 (M+, 0.3), 144 (2), 126 (16), 109 (24), 97 (52), 83 (61), 69 (88), 55 (100). ESI-HRMS calcd for C10112302 [M+H].sup.+: 175.16926; found: 175.16928.

    [0139] It is to be understood that the metal-catalyzed alkoxycarbonylation of lactone is not limited to the specific embodiments described above, but encompasses any and all embodiments within the scope of the generic language of the following claims enabled by the embodiments described herein, or otherwise shown in the drawings or described above in terms sufficient to enable one of ordinary skill in the art to make and use the claimed subject matter.