Bipyridyl compound
09908852 ยท 2018-03-06
Assignee
Inventors
- Yoichiro Kuninobu (Bunkyo-ku, JP)
- Motomu Kanai (Bunkyo-ku, JP)
- Haruka Ida (Suginami-ku, JP)
- Mitsumi Nishi (Taito-ku, JP)
Cpc classification
B01J31/1815
PERFORMING OPERATIONS; TRANSPORTING
B01J2231/4277
PERFORMING OPERATIONS; TRANSPORTING
International classification
Abstract
There are provided a compound capable of being a novel ligand allowing regioselective borylation to be performed in the aromatic borylation reaction, and a catalyst using the same compound. There is provided a bipyridyl compound represented by a general formula (1): (wherein A represents a single bond, a vinylene group or an ethynylene group; X represents an oxygen atom or a sulfur atom; n pieces of R.sup.1 may be the same or different, and R.sup.1 represents a hydrogen atom, a halogen atom, an optionally substituted hydrocarbon group, an optionally substituted alkoxy group, an optionally substituted aryloxy group, an optionally substituted amino group, a cyano group, a nitro group, or an alkoxycarbonyl group, or two adjacent R.sup.1 may form a saturated or unsaturated ring structure optionally containing a hetero atom together with the carbon atoms bonded to the two R.sup.1; R.sup.2 represents a hydrogen atom, an optionally substituted hydrocarbon group, an optionally substituted alkoxy group, or an optionally substituted aryloxy group; and n represents a number of 1 to 4). ##STR00001##
Claims
1. A bipyridyl compound selected from the group consisting of 1-(2-([2,2-Bipyridin]-5-yl)phenyl)-3-cyclohexylurea, 1-(2-([2,2-Bipyridin]-5-yl)phenyl)-3-hexylurea, 1-(2-([2,2-Bipyridin]-5-yl)phenyl)-3-(4-trifluoromethylphenyl)urea, 1-(2-([2,2-Bipyridin]-5-yl)phenyl)-3-(4-butylphenyl)urea, and 1-(2-([2,2-Bipyridin]-5-yl)phenyl)-3-(2,6-dimethylphenyl)urea.
2. The bipyridyl compound according to claim 1, which is 1-(2-([2,2-Bipyridin]-5-yl)phenyl)-3-cyclohexylurea.
3. The bipyridyl compound according to claim 1, which is 1-(2-([2,2-Bipyridin]-5-yl)phenyl)-3-hexylurea.
4. The bipyridyl compound according to claim 1, which is 1-(2-([2,2-Bipyridin]-5-yl)phenyl)-3-(4-trifluoromethylphenyl)urea.
5. The bipyridyl compound according to claim 1, which is 1-(2-([2,2-Bipyridin]-5-yl)phenyl)-3-(4-butylphenyl)urea.
6. The bipyridyl compound according to claim 1, which is 1-(2-([2,2-Bipyridin]-5-yl)phenyl)-3-(2,6-dimethylphenyl)urea.
Description
EXAMPLES
(1) Next, the present invention is described in detail with, reference to Examples, but the present invention is not limited by these Examples at all.
Example 1
(1) 2-([2,2-Bipyridin]-5-yl) aniline
(2) ##STR00004##
(3) 2-Bromaniline (0.566 mL, 5.00 mmol, 1 equiv) was dissolved, in 10 mL of dioxane 10 mL, and to the resulting solution, triethylamine (2.80 mL, 20.0 mmol, 4 equiv), PdCl.sub.2 (dppf) (183 mg, 0.250 mmol, 5 mol %) and pinacolborane (2.2 mL, 15.0 mmol, 3 equiv) were added and stirred at 100 C. for 4 hours. The reaction solution was cooled to room temperature, 2.2 mL of water, Ba(OH).sub.2.8H.sub.2O (4.73 g, 15.0 mmol, 3 equiv) and 5-bromo-2,2-bipyridine (1.08 g, 4.60 mmol, 0.92 equiv) were added to the reaction solution, and then further stirred at 100 C. for 4 hours. The reaction solution was cooled to room temperature, then filtered with Celite, and washed with 120 mL of ethyl acetate. The filtrate was subjected to separatory washing with 120 mL of water, dried with anhydrous sodium sulfate, and then filtered; the solvent was removed under reduced pressure to yield a crude product. By using a silica gel pretreated with a 20% triethylamine-hexane solution (200 mL), the crude product was subjected to a column purification (hexane/ethyl acetate=3/1). Thus, 672 mg (yield: 59%) of a white solid was obtained.
(4) 59% yield; white solid; R.sub.f=0.50 (hexane/ethyl acetate=1/1); .sup.1H NMR (400 MHz, CDCl.sub.3) 3.77 (s, 2H), 6.81 (d, J=7.8 Hz, 1H), 6.88 (d, J=7.5 Hz, 1H), 7.17 (d, J=7.5 Hz, 1H), 7.22 (d, J=7.8 Hz, 1H), 7.33 (d, J=7.8, 5.2 Hz, 1H), 7.84 (dd, J=7.8, 7.8 Hz, 1H), 7.96 (d, J=8.2 Hz, 1H), 8.43 (d, J=7.8 Hz, 1H), 8.47 (d, J=8.2 Hz, 1H), 8.71 (d, J=5.2 Hz, 1H), 8.80 (s, 1H); .sup.13C NMR (100 MHz, CDCl.sub.3) 116.0, 119.0, 121.0, 121.1, 123.6, 123.8, 129.5, 130.6, 135.3, 137.0, 137.5, 143.9, 149.3, 149.5, 154.9, 156.0; IR (KBr, /cm.sup.1) 3346, 3219, 1459, 1357, 1240, 1094, 994, 858, 751, 644; HRMS (ESI.sup.+) Calcd for C.sub.16H.sub.13N.sub.3Na ([M+Na].sup.+) 270.1002, Found 270.1007.
(2) 1-(2-[(2,2-Bipyridin]-5-yl)phenyl)-3-cyclohexylurea
(5) ##STR00005##
(6) 2-([2,2-Bipyridin]-5-yl) aniline (371 mg, 1.5 mol, 1.0 equiv), isocyanatecyclohexane (0.29 mL, 2.3 mmol, 1.5 equiv) were dissolved in 5.0 mL of dichlororomethane, and stirred at room temperature for 24 hours. The solvent was removed under reduced pressure from the reaction solution to yield a crude product. By recrystallization (hexane/dichloromethane), 281 mg (yield: 50%) of a target product was obtained.
(7) 50% yield; white solid; R.sub.f=0.53 (hexane/ethyl acetate=1/2); .sup.1H NMR (400 MHz, CDCl.sub.3) 0.94-1.10 (m, 3H), 1.27-1.34 (m, 3H), 1.52-1.67 (m, 2H), 1.86-1.89 (m, 2H), 3.51-3.59 (m, 1H), 4.86-4.97 (m, 1H), 6.26-6.35 (m, 1H), 7.21 (dd, J=7.2, 6.3 Hz, 1H), 7.30 (d, J=6.3 Hz, 1H), 7.35 (dd, J=7.2, 7.2 Hz, 1H), 7.42 (d, J=7.2 Hz, 1H), 7.84-7.87 (m, 2H), 7.92 (d, J=8.6 Hz, 1H), 8.39 (d, J=8.0 Hz, 1H), 8.44 (d, J=3.6 Hz, 1H), 8.69-8.71 (m, 2H); .sup.13C NMR (125 MHz, CDCl.sub.3) 25.0, 25.6, 33.7, 49.2, 121.1, 121.3, 122.5, 123.8, 124.1, 129.0, 129.6, 130.4, 134.8, 136.6, 137.2, 137.9, 149.4, 149.5, 154.8, 155.1, 155.5; IR (KBr, /cm.sup.1) 3245, 3219, 1453, 1.367, 1240, 1094, 994, 858, 751, 644; HEMS (ESI.sup.+) Calcd for C.sub.23H.sub.24N.sub.4NaO ([M+Na].sup.+) 395.1842, Found 395.1850.
Examples 2 to 8
(8) The following compounds were synthesized in the same manner as Example 1.
Example 2
1-(2-([2,2-Bipyridin]-5-yl)phenyl)-3-hexylurea
(9) ##STR00006##
(10) 62% yield; white solid; R.sub.f=0.32 (hexane/ethyl acetate=1/1); .sup.1H NMR (500 MHz, CDCl.sub.3) 0.79 (t, J=6.9 Hz, 3H), 1.16-1.22 (m, 6H), 1.33-1.38 (m, 20), 3.14 (td, J=7.2, 7.2 Hz, 2H), 5.48 (brs, 1H), 6.70 (s, 1H), 7.12-7.20 (m, 2H), 7.32 (dd, J=6.3, 4.6, 1.2 Hz, 1H), 7.39 (ddd, J=6.3, 4.8, 1.1 Hz, 1H), 7.69 (ddd, J=8.5, 7.6, 2.2 Hz, 1H), 7.81 (ddd, J=7.7, 7.6, 1.6 Hz, 1H), 8.06 (d, J=8.1 Hz, 1H), 8.15 (d, J=8.5 Hz, 1H), 8.19 (d, J=8.1 Hz, 1H), 8.56 (d, J=2.2 Hz, 1H), 8.64 (dd, J=4.0, 1.1 Hz, 1H); .sup.13C NMR (125 MHz, CDCl.sub.3) 14.0, 22.5, 26.6, 30.0, 31.5, 40.2, 120.9, 121.1, 122.3, 123.2, 124.0, 128.4, 129.4, 130.1, 135.1, 136.9, 137.1, 137.1, 149.1, 149.4, 154.3, 155.2, 156.1; IR (KBr, /cm.sup.31 1) 3292, 2922, 2855, 1626, 1457, 1371, 1266, 1090, 856, 649; HRMS (ESI.sup.+) Calcd for C.sub.23H.sub.26N.sub.4NaO ([M+Na].sup.+) 397.1999, Found 397.1997.
Example 3
1-(2-([2,2-Bipyridin]-5-yl)phenyl)-3-(4-methoxyphenyl)urea
(11) ##STR00007##
(12) 6.5% yield; white solid; R.sub.f=0.50 (hexane/ethyl acetate=1/2); .sup.1H NMR (400 MHz, CDCl.sub.3) 3.62 (s, 3H) 6.71 (d, J=8.6 Hz, 2H), 6.98 (d, J=8.6 Hz, 2H), 7.20-7.22 (m, 1H), 7.36-7.38 (m, 3H), 7.46-7.49 (m, 1H), 7.54 (s, 1H), 7.81 (dd, J=8.0, 2.0 Hz, 1H), 7.89 (ddd, J=8.0, 7.7, 1.7 Hz, 1H), 7.94-7.96 (m, 1H), 8.44 (d, J=3.0 Hz, 1H), 8.46 (d, J=8.0 Hz, 1H), 8.63 (d, J=1.7 Hz, 1H), 8.73 (d, J=4.6 Hz, 1H); .sup.13C NMR (125 MHz, DMSO-d.sub.6) 55.6, 114.1, 120.4, 121.0, 124.7, 127.8, 129.2, 130.2, 130.6, 132.0, 135.5, 137.7, 137.1, 137.6, 137.9, 149.3, 149.8, 154.2, 155.3, 157.2, 181.4; IR (KBr, /cm.sup.1) 3278, 1636, 1509, 1458, 1370, 1244, 1111, 855, 756, 649; HRMS (ESI.sup.+) Calcd for C.sub.24H.sub.20N.sub.4NaO.sub.2 ([M+Na].sup.+) 419.1478, Found 419.1458.
Example 4
1-(2-([2,2-Bipyridin]-5-yl)phenyl)-3-(4-trifluoromethylphenyl)urea
(13) ##STR00008##
(14) 50% yield; pale yellow solid; R.sub.f=0.63 (hexane/ethyl acetate=1/2); .sup.1H NMR (400 MHz, CDCl.sub.3) 7.10-7.16 (m, 2H), 7.35-7.53 (m, 7H), 7.64 (d, J=8.1 Hz, 1H), 7.84-7.85 (m, 2H), 8.22 (brs, 1H), 8.42 (d, J=8.3 Hz, 1H), 8.52 (d, J=1.3 Hz, 1H), 8.57 (d, J=3.1 Hz, 1H), 9.35 (brs, 1H); .sup.13C HMR (125 MHz, CDCl.sub.3) 118.1, 118.7, 121.1, 121.3, 123.2, 123.6 (q, J=33.6 Hz), 124.3 (q, J=271 Hz), 124.5, 126.1 (q, J=3.6 Hz), 127.2, 120.9, 130.3, 135.8, 136.9, 137.7, 138.6, 143.0, 149.5, 150.1, 153.2, 153.5, 154.3; .sup.19F NMR (368 MHz, CDCl.sub.3) 63.8 (s, 3F); IR (KBr, /cm.sup.1) 3331, 3058, 1716, 1654, 1449, 1329, 1165, 1014, 842, 759; HRMS (ESI.sup.+) Calcd for C.sub.24H.sub.17F.sub.3N.sub.4NaO ([M+Na].sup.+) 457.1247, Found 457.1252.
Example 5
1-(2-([2,2-Bipyridin]-5-yl)phenyl)-3-(4-butylphenyl)urea
(15) ##STR00009##
(16) 27% yield; white solid; R.sub.f=0.64 (hexane/ethyl acetate=1/2); .sup.1H NMR (400 MHz, CDCl.sub.3) 0.85 (t, J=7.5 Hz, 3H), 1.20-1.28 (m, 2H), 1.38-1.46 (m, 2H), 2.38 (t, J=7.7 Hz, 2H), 6.94 (d, J=1.9 Hz, 2H), 7.05-7.15 (m, 4H), 7.34 (dd, J=7.2, 4.9 Hz, 1H), 7.41 (ddd, J=7.7, 7.7, 1.7 Hz, 1H), 7.59 (d, J=8.0 Hz, 1H), 7.82 (dd, J=7.2, 7.2 Hz, 1H), 8.01-8.03 (m, 1H), 8.15-8.16 (m, 1H), 8.30 (d, J=8.6 Hz, 1H), 8.52 (s, 1H), 8.65 (d, J=4.6 Hz, 1H); .sup.13C HMR (125 MHz, CDCl.sub.3) 14.0, 22.4, 33.7, 35.0, 120.6, 121.0, 121.3, 121.4, 123.2, 124.2, 127.8, 129.0, 129.6, 130.2, 133.1, 136.2, 136.8, 137.3, 138.1, 138.3, 149.4, 149.7, 153.6, 154.4, 1.55.0; IR (KBr, /cm.sup.1) 3293, 1.637, 1546, 1509, 1458, 1372, 1246, 1122, 799, 757; HRMS (ESI.sup.+). Calcd for C.sub.27H.sub.26N.sub.4NaO ([M+Na].sup.+) 445.1999, Found 445.1989.
Example 6
1-(2-([2,2-Bipyridin]-5-yl)phenyl)-3-(2,6-dimethylphenyl) urea
(17) ##STR00010##
(18) 58% yield; white solid; R.sub.f=0.30 (hexane/ethyl acetate=1/1); .sup.1H NMR (400 MHz, CDCl.sub.3) 2.15 (s, 6H), 5.73 (s, 1H), 6.19 (s, 1H), 6.78-6.30 (m, 1H), 6.34 (d, J=6.7 Hz, 2H), 7.13-7.18 (m, 2H), 7.36-7.44 (m, 2H), 7.48 (d, J=7.6 Hz, 1H), 7.89 (ddd, J=7.6, 7.6, 1.8 Hz, 1H), 8.23 (d, J=8.1 Hz, 1H), 8.29 (d, J=8.5 Hz, 1H), 8.39 (s, 1H), 8.43 (d, J=8.1 Hz, 1H), 8.75 (d, J=4.9 Hz, 1H); .sup.13C NMR (125 MHz, CDCl.sub.3) 18.3, 120.9, 121.1, 124.1, 128.4, 128.5, 129.0, 1.29.0, 130.0, 132.8, 133.3, 136.1, 137.0, 137.1, 137.3, 149.1, 149.5, 154.1, 155.3, 155.6, 155.7, 157.0; IR (KBr, /cm.sup.1) 3265, 1632, 1550, 1457, 1371, 1240, 1002, 855, 797, 717; HRMS (ESI.sup.+) Calcd for C.sub.25H.sub.22N.sub.4NaO ([M+Na].sup.+) 417.1686, Found 417.1679.
Example 7
1-(2-([2,2-Bipyridin]-5-yl)phenyl)-3-cyclohexylthiourea
(19) ##STR00011##
(20) 51% yield; white solid; R.sub.f=0.36 (hexane/ethyl acetate=1/1); .sup.1H NMR (400 MHz, CDCl.sub.3) 0.96-1.12 (m, 3H), 1.24-1.37 (m, 2H), 1.55-1.63 (m, 4H), 1.90-1.93 (m, 2H), 4.14 (s, 1H), 5.71 (s, 1H), 7.30-7.34 (m, 2H), 7.41-7.54 (m, 3H), 7.82 (d, J=8.1 Hz, 1H), 7.85 (ddd, J=8.1, 8.1, 2.2 Hz, 1H), 8.40 (d, J=0.1 Hz, 1H), 8.47 (d, J=9.0 Hz, 1H), 8.68-8.73 (m, 2H); .sup.13C NMR (100 MHz, CDCl.sub.3) 24.8, 25.5, 32.7, 54.1, 121.1, 121.4, 124.0, 127.9 (2C), 128.6, 130.0, 131.6, 133.6, 135.3, 137.0 (2C), 148.9, 149.4, 155.7, 155.8, 179.5; IR (KBr, /cm.sup.1) 3293, 2931, 2857, 1637, 1458, 1373, 1229, 1001, 841, 656; HRMS (ESI.sup.+). Calcd for C.sub.23H.sub.24N.sub.4NaS ([M+Na].sup.+) 411.1619, Found 411.1611.
Example 8
1-2-([2,2-Bipyridin]-5-ylethynyl)aniline
(21) ##STR00012##
(22) A triethylamine (1.3 mL) solution of PdCl.sub.2(PPh.sub.3).sub.2 (1.8 mg, 2.5 mol, 0.5 mol %), CuI (1.0 mg, 5.0 mol, 1.0 mol %) and 5-bromo-2,2-bipyridine (118 mg, 0.50 mmol, 1 equiv) was stirred for 15 minutes at room temperature. To the resulting solution, 2-ethylaniline (93 L, 0.6 mmol, 1.2 equiv) was added, and then stirred at 70 C. for 3.5 hours. The temperature of the solution was cooled to room temperature, then the solid substances were removed by filtration with Celite, and the obtained filtrate was washed with water (20 mL) and was subjected to extraction with diethyl ether (320 mL). The crude product was isolated and purified by silica gel column chromatography (hexane/ethyl acetate=3/1), and thus 106 mg (yield: 78%) of a target product was obtained as a white solid.
(23) 78% yield; white solid; R.sub.f=0.15 (hexane/ethyl acetate=3/1); .sup.1H mm (400 MHz, CDCl.sub.3) 4.32 (brs, 2H), 6.72-6.77 (m, 2H), 7.18 (dt, J=7.6, 1.3 Hz, 1H), 7.34 (dd, J=7.6, 4.9 Hz, 1H), 7.40 (dd, J=8.1, 1.8 Hz, 1H), 7.84 (dd, J=7.6, 7.6 Hz, 1H), 7.93 (dd, J=8.1, 2.2 Hz, 1H), 8.41-8.44 (m, 2H), 8.70 (d, J=4.0 Hz, 1H), 8.81 (dd, J=8.2, 1.8 Hz, 1H); .sup.13C NMR (125 MHz, CDCl.sub.3) 90.4, 91.8, 107.3, 114.6, 118.2, 120.5 (2C), 121.5, 124.0, 130.4, 132.5, 137.1, 139.2, 148.1, 149.4, 151.5, 154.9, 155.6; IE (KBr, /cm.sup.1). 3313, 2362, 2206, 1624, 1569, 1488, 1459, 1312, 1093, 739; HRMS (ESI.sup.+) Calcd for C.sub.18H.sub.13N.sub.3Na ([M+Na].sup.+) 294.1007, Found 294.0999.
(2) 1-(2-([2,2-Bipyridin]-5-ylethynyl)phenyl)-3-phenylurea
(24) ##STR00013##
(25) The target product was produced in the same manner as Example 1 (2).
(26) 46% yield; white solid; R.sub.f=0.29 (ethyl acetate); .sup.1H NMR (500 MHz, CDCl.sub.3) 6.49 (brs, 1H), 7.04-7.10 (m, 3H), 7.29-7.30 (m, 1H), 7.34-7.41 (m, 4H), 7.47-7.49 (m, 2H), 7.58 (d, J=6.3 Hz, 1H), 7.86 (dd, J=5.8, 5.8 Hz, 1H), 8.30 (d, J=6.7 Hz, 1H), 8.37 (d, J=10.2 Hz, 1H), 8.44 (d, J=6.3 Hz, 1H), 8.56 (s, 1H), 8.72 (d, J=3.6 Hz, 1H); .sup.13C NMR (125 MHz, CDCl.sub.3) 88.8, 92.7, 111.4, 119.4, 134.4, 120.4, 121.6, 122.8, 123.4, 124.3, 125.7, 127.7, 129.8, 130.5, 132.2, 137.2, 139.5, 139.9, 149.5, 151.7, 153.0, 155.3; 153.4; IR (KBr, /cm.sup.) 8299, 1844, 1576, 1552, 1458, 1296, 1091, 794, 743, 692; HRMS (ESI.sup.+) Calcd for C.sub.25H.sub.18N.sub.4NaO ([M+Na].sup.+) 413.1378, Found 413.1388.
Example 9
(27) (1) Meta-Selective Borylation of an Aromatic Compound with an Iridium Catalyst
(28) In a dried test tube, to a p-xylene (1.5 mL) solution of N,N-dihexylbenzamide (72.4 mg, 0.250 mmol, 1.00 equiv), [Ir(OMe) (cod)].sub.2 (1.2 mg, 1.9 mol, 0.75 mol %), 1-(2-([2,2-bipyridin]-5-yl)phenyl)-3-cyclohexylurea (1.2 mg, 3.8 mol, 1.5 mol %) and bis(pinacolato)diboron (47.6 mg, 0.188 mmol, 0.750 equiv) were added and stirred at 25 C. for 24 hours. The solvent was removed under reduced pressure, and then the products were isolated and prepared by recycling preparative HPLC.
(29) ##STR00014##
(30) The obtained compounds were as follows.
N,N-Dihexyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide
(31) ##STR00015##
(32) 40% yield; colorless oil; .sup.1H NMR (500 MHz, CDCl.sub.3) 0.82 (t, J=6.9 Hz, 3H), 0.89-0.92 (m, 3H), 1.10-1.21 (m, 6H), 130-141 (m, 18H), 1.46-1.50 (m, 2H), 1.65-1.66 (m, 2H), 3.15 (t, J=6.9 Hz, 2H), 3.46 (t, J=7.2 Hz, 2H), 7.38 (dd, J=8.0, 7.2 Hz, 1H), 7.43 (ddd, J=8.0, 1.7, 1.7 Hz, 1H), 7.78 (s, 1H), 7.80 (ddd, J=7.2, 1.7, 1.7 Hz, 1H); .sup.13C NMR (100 MHz, CDCl.sub.3) 14.1, 14.2, 22.6, 22.8, 25.0, 26.3, 26.9, 27.6, 28.8, 31.4, 31.8, 45.0, 49.2, 84.1, 127.8, 129.3, 132.7, 135.4, 136.8, 171.8; .sup.11B NMR. (130 MHz, CDCl.sub.3) 30.2; IR (neat, /cm.sup.1) 2930, 2858, 1626, 1411, 1358, 1319, 1144, 861, 754, 666; HRMS (ESI.sup.+). Calcd for C.sub.25H.sub.42BNNaO.sub.3 ([M+Na].sup.+) 438.3150, Found 438.3151.
N,N-Dihexyl-4-(4,4,5,5-tetrarmethyl-1,3,2-dioxaborolan-2-yl)benzamide
(33) ##STR00016##
(34) 3.3% yield; colorless oil; .sup.1H HMR (500 MHz, CDCl.sub.3) 0.82 (t, J=7.2 Hz, 3H), 0.89-0.92 (m, 3H), 1.06-1.11 (m, 4H), 1.18-1.25 (m, 2H), 1.35-1.36 (m, 18H), 1.46-1.47 (m, 2H), 1.63-1.66 (m, 2H), 3.13 (t, J=6.9 Hz, 2H), 3.46 (t, J=7.2 Hz, 2H), 7.32 (d, J=8.3 Hz, 2H), 7.81 (d, J=8.3 Hz, 2H); .sup.13C NMR (125 MHz, CDCl.sub.3), 14.0, 14.1, 22.5, 22.7, 25.0, 26.3, 28.8, 27.6, 28.7, 31.4, 31.7, 44.8, 49.0, 84.1, 125.7, 134.8, 140.1, 171.6; .sup.11B NMR (130 MHz, CDCl.sub.3) 29.9; IR (neat, /cm.sup.1) 2929, 1636, 1511, 1396, 1360, 1322, 1144, 1108, 859, 659; HRMS (ESI.sup.+) Calcd for C.sub.25H.sub.42BNNaO.sub.3 ([M+Na].sup.+) 438.3150, Found 438.3170.
N,N-Dihexyl-3,5-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide
(35) ##STR00017##
(36) 3.0% yield; colorless oil; .sup.1H NMR (500 MHz, CDCl.sub.3) 0.81 (t, J=7.2 Hz, 3H), 0.90-0.93 (m, 3H), 1.10-1.27 (m, 10H), 1.31-1.35 (m, 28H), 1.62-1.66 (m, 2H), 3.12 (t, J=6.9 Hz, 2H), 3.44 (t, J=7.2 Hz, 2H), 7.88 (s 2H), 8.26 (s, 1H); .sup.13C NMR (100 MHz, CDCl.sub.3) 14.1, 14.2, 22.5, 22.8, 25.0, 26.3, 27.0, 27.7, 28.9, 31.4, 31.8, 45.0, 49.3, 84.0, 135.5, 136.3, 141.7, 171.7; .sup.11B: NMR (130 MHz, CDCl.sub.3) 32.9; IR (neat, /cm.sup.1) 2929, 1628, 1329, 1265, 1142, 967, 889, 801, 755, 718; HRMS (ESI.sup.+) Calcd for C.sub.31H.sub.53B.sub.2NNaO.sub.5 ([M+Na].sup.+) 564.4002, Found 564.4021.
(37) By using the ligand used in (1), the following compounds ((2) to (27)) were obtained in the same manner as the method of (1).
(2) N,N-Dihexyl-2-methoxy-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2yl)benzamide and N,N-dihexyl-2methoxy-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide
(38) ##STR00018##
(39) 63% yield [meta/para=7.5]; colorless oil; .sup.11B NMR (130 MHz, CDCl.sub.3) 31.9; IR (neat, /cm.sup.1) 2930, 1627, 1410, 1355, 1140, 1027, 965, 851, 754, 683; HRMS (ESI.sup.+) Calcd for C.sub.25H.sub.44BNNaO.sub.4 ([M+Na].sup.+) 468.3256, Found 468.3246.
(40) N,N-Dihexyl-2-methoxy-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide: .sup.1H NMR (400 MHz, CDCl.sub.3) 0.80 (t, J=7.4 Hz, 3H), 0.91 (t, J=6.7 Hz, 3H), 1.06-1.08 (m, 4H), 1.16-1.50 (m, 22H), 1.62-1.64 (m, 2H), 3.01-3.04 (m, 2H), 3.48-3.49 (m, 2H), 3.82 (s, 3H), 6.87 (d, J=8.3 Hz, 1H), 7.63 (s, 1H), 7.76 (d, J=8.3 Hz, 1H); .sup.13C NMR (125 MHz, CDCl.sub.3) 14.1, 14.2, 22.5, 22.8, 24.7, 26.3, 26.7, 27.6, 28.4, 31.4, 31.8, 44.4, 48.5, 55.4, 83.7, 110.1, 126.6, 134.4, 137.0, 157.8, 169.2.
(41) N,N-Dihexyl-2-methoxy-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide: .sup.1H NMR (400 MHz, CDCl.sub.3) 0.80 (t, J=7.4 Hz, 3H), 0.91 (t, J=6.7 Hz, 3H), 1.06-1.08 (m, 4H), 1.18-1.50 (m, 20H), 1.62-1.64 (m, 4H), 3.01-3.04 (m, 2H), 3.48-3.49 (m, 2H), 3.85 (s, 3H), 7.17 (d, J=7.2 Hz, 1H), 7.29 (s, 1H), 7.41 (d, J=7.2 Hz, 1H); .sup.13C NMR (125 MHz, CDCl.sub.3) 14.1, 14.2, 22.5, 22.8, 25.0, 26.3, 26.8, 27.5, 28.4, 31.4, 31.8, 44.3, 48.3, 55.6, 84.1, 116.4, 127.1, 127.4, 130.0, 154.6, 169.2.
3) N,N-Dihexyl-2-methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide and N,N-dihexyl-2-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide
(42) ##STR00019##
(43) 39% yield [meta/para=15]; colorless oil; IR (neat, /cm.sup.1) 2929, 1634, 1466, 1357, 1145, 1105, 965, 862, 754, 686; HRMS (ESI.sup.+) Calcd for C.sub.26H.sub.44BNNaO.sub.3 ([M+N].sup.+) 452.3306, Found 452.3306.
(44) N,N-Dihexyl-2-methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide: .sup.1H NMR (500 MHz, CDCl.sub.3) 0.82 (t, J=7.2 Hz, 3H), 0.91 (t, J=6.9 Hz, 3H), 1.07-1.11 (m, 4H), 1.14-1.21 (m, 2H), 1.25-1.39 (m, 18H), 1.41-1.47 (m, 2H), 1.62-1.70 (m, 2H), 2.29 (s, 3H), 3.01-3.05 (m, 2H), 3.39-3.56 (m, 2H), 7.19 (d, J=7.5 Hz, 1H), 7.59 (s, 1H), 7.67 (d, J=7.5 Hz, 1H); .sup.13C NMR (125 MHz, CDCl.sub.3) 14.1, 14.2, 19.4, 22.5, 22.8, 25.0, 26.3, 27.0, 27.7, 28.5, 31.3, 31.8, 44.6, 48.6, 83.9, 129.8, 132.3, 134.9, 136.8, 137.4, 171.3; .sup.11B NMR (130 MHz, CDCl.sub.3) 30.5;
(45) N,N-Dihexyl-2-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide: .sup.1H NMR (500 MHz, CDCl.sub.3) 0.81 (t, J=7.2 Hz, 3H), 0.90 (t, J=6.0 Hz, 3H), 1.04-1.11 (m, 4H), 1.14-1.26 (m, 2H), 1.28-1.47 (m, 20H), 1.62-1.67 (m, 2H), 2.27 (s, 3H), 2.85-3.15 (m, 2H), 3.20-3.75 (m, 2H), 7.14 (d, J=7.8 Hz, 1H), 7.62 (d, J=7.8 Hz, 1H), 7.64 (s, 1H); .sup.13C NMR (125 MHz, CDCl.sub.3) 14.1, 14.2, 18.9, 22.6, 22.8, 25.0, 26.4, 27.0, 27.6, 28.5, 31.4, 31.8, 44.4, 48.4, 84.1, 125.3, 132.2, 133.2, 136.7, 140.1, 171.2; .sup.11B NMR (130 MHz, CDCl.sub.3) 31.3.
(4) 2-Bromo-N,N-dihexyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide and 2-bromo-N,N-dihexyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide
(46) ##STR00020##
(47) 91% yield [meta/para=8.6]; colorless oil; .sup.11B NMR (130 MHz, CDCl.sub.3) 30.0; IR (neat, /cm.sup.1) 2929, 1640, 1590, 1355, 1144, 1094, 964, 839, 754, 688; HRMS (ESI.sup.+) Calcd for C.sub.25H.sub.41BBrNNaO.sub.3 ([M+N].sup.+) 516.2255, Found 516.2245. 2-Bromo-N,N-dibexyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide: .sup.1H NMR (400 MHz, CDCl.sub.3) 0.80 (t, J=7.2 Hz, 3H), 0.91 (t, J=6.7 Hz, 3H), 1.07-1.10 (m, 4H), 1.16-1.20 (m, 2H), 1.32-1.34 (m, 16H), 1.45-1.59 (m, 4H), 1.66-1.68 (m, 2H), 3.01-3.08 (m, 2H), 3.22-3.29 (m, 1H), 3.66-3.73 (m, 1H), 7.55 (d, J=7.9 Hz, 1H), 7.61 (dd, J=7.9, 1.4 Hz, 1H), 7.67 (d, J=1.4 Hz, 1H); .sup.13C NMR (125 MHz, CDCl.sub.3) 14.0, 14.2, 22.4, 22.7, 24.8 (br), 26.2, 26.9, 27.3, 28.3, 31.3, 31.7, 44.6, 48.3, 84.2, 122.8, 132.1, 134.2, 135.9, 138.4, 168.9.
(48) 2-Bromo-N,N-dibexyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide: .sup.1H NMR (400 MHz, CDCl.sub.3) 0.80 (t, J=7.2 Hz, 3H), 0.91 (t, J=6.7 Hz, 3H), 1.07-1.10 (m, 4H), 1.16-1.20 (m, 2H), 1.32-1.34 (m, 16H), 1.45-1.59 (m, 4H), 1.66-1.68 (brs, 2H), 3.01-3.08 (m, 2H), 3.22-3.29 (m, 1H), 3.66-3.73 (m, 1H), 7.23 (d, J=7.4 Hz, 1H), 7.73 (dd, J=7.4, Hz, 1H), 7.98 (s, 1H); .sup.13C NMR (125 MHz, CDCl.sub.3) 14.0, 14.2, 22.5, 22.7, 24.9 (br), 26.3, 26.9, 27.2, 28.3, 31.2, 31.7, 44.7, 48.5, 84.4, 119.1, 127.3, 133.6, 138.7, 141.3, 168.8.
(5) 2-Chloro-N,N-dihexyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide and 2-chloro-N,N-dihexyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide
(49) ##STR00021##
(50) 84% yield [meta/para=12]; pale yellow oil; HRMS (ESI.sup.+). Calcd for C.sub.25H.sub.41BClNNaO.sub.3 ([M+N].sup.+) 472.2760, Found 472.2764.
(51) 2-Chloro-N,N-dihexyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide: .sup.1H NMR (400 MHz, CDCl.sub.3) 0.80 (t, J=7.2 Hz, 3H), 0.91 (t, J=6.7 Hz, 3H), 1.08-1.19 (m, 6H), 1.25-1.61 (m, 20H), 1.63-1.69 (m, 2H), 2.98-3.12 (m, 2H), 3.28-3.34 (m, 1H), 3.64-3.70 (m, 1H), 7.36 (d, J=8.5 Hz, 1H), 7.69 (s, 1H), 7.70 (d, J=8.5 Hz, 1H); .sup.13C NMR (125 MHz, CDCl.sub.3) 14.1, 14.2, 19.4, 22.5, 22.8, 24.8, 26.3, 26.9, 27.4, 28.4, 31.3, 31.8, 44.7, 48.5, 84.3, 129.0, 133.5, 134.3, 136.0, 136.4, 168.2; .sup.11B NMR (130 MHz, CDCl.sub.3) 32.1; IR (neat, /cm.sup.1) 2929, 2857, 1645, 1507, 1456, 1387, 1144, 1095, 963, 732.
(52) 2-Chloro-N,N-dihexyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide: .sup.1H NMR (400 MHz, CDCl.sub.3) 0.81 (t, J=7.2 Hz, 3H), 0.90 (t, J=6.5 Hz, 3H), 1.07-1.20 (m, 6H), 1.25-1.51 (m, 20H), 1.65-1.67 (m, 2H), 2.98-3.12 (m, 2H), 3.19-3.26 (m, 1H), 3.71-3.79 (m, 1H), 7.25 (d, J=7.6 Hz, 1H), 7.69 (d, J=7.6 Hz, 1H), 7.80 (s, 1H); .sup.13C NMR (125 MHz, CDCl.sub.3) 14.1, 14.2, 22.5, 22.8, 25.0, 26.4, 26.9, 27.3, 28.4, 31.4, 31.8, 44.6, 48.5, 84.3, 127.4, 132.2, 133.1, 135.7, 139.3, 168.1; .sup.11B NMR (130 MHz, CDCl.sub.3) 30.2; IR (neat, /cm.sup.1) 2929, 2857, 1644, 1498, 1456, 1355, 1143, 1096, 1047, 686.
(6N,N-Dihexyl-5-(4,4,5,5-tetrarmethyl-1,3,2-dioxaborolan-2-yl)-2-(trifluoromethyl)benzamide
(53) ##STR00022##
(54) 93.0% yield; colorless oil; .sup.1H NMR (500 MHz, CDCl.sub.3) 0.80 (t, J=7.2 Hz, 3H), 0.91 (t, J=6.7 Hz, 3H), 1.07-1.22 (m, 6H), 1.33-1.49 (m, 20H), 1.64-1.65 (m, 2H), 2.88-3.04 (m, 2H), 3.13-3.23 (m, 1H), 3.69-3.79 (m, 1H), 7.65 (d, J=7.9 Hz, 1H), 7.75 (s 1H), 7.88 (d, J=7.9 Hz, 1H); .sup.13C NMR (100 MHz, CDCl.sub.3) 14.1, 22.4, 22.7, 24.9, 26.2, 26.8, 27.0, 28.0, 31.3, 31.7, 31.8, 44.5, 48.8, 84.5, 123.8 (q, J=275 Hz), 125.6, (q, J=4.8 Hz), 127.1, 128.7 (q, J=31.2 Hz), 133.8, 134.9, 168.6; .sup.19F NMR (368 MHz, CDCl.sub.3) 62.0; .sup.11B NMR (130 MHz, CDCl.sub.3) 30.5; IR (neat, /cm.sup.1) 2930, 2859, 1644, 1505, 1467, 1312, 1102, 1041, 844, 690; HRMS (ESI.sup.+) Calcd for C.sub.26H.sub.41BF.sub.3NNaO.sub.3 ([M+Na].sup.+) 506.3024, Found 506.3018.
(7) N,N-Dihexyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2yl)-2-(trifluoromethoxy)benzamide and N,N-dihexyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-(trifluoromethoxy)benzamide
(55) ##STR00023##
(56) 92% yield [meta/para=6.8]; colorless oil; .sup.13F NMR (368 MHz, CDCl.sub.3) 58.6; .sup.11B NMR (130 MHz, CDCl.sub.3) 30.2; IR (neat, /cm.sup.1) 2931, 2859, 1644, 1468, 1359, 1255, 1003, 965, 850, 687; HRMS (ESI.sup.+) Calcd for C.sub.26H.sub.41BF.sub.3NNaO.sub.4 ([M+Na].sup.+) 522.2973, Found 522.2996.
(57) N,N-Dihexyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-(trifluoromethoxy)benzamide: .sup.1H NMR (400 MHz, CDCl.sub.3) 0.80 (t, J=7.2 Hz, 3H), 0.90 (t, J=6.7 Hz, 3H), 1.08-1.09 (m, 4H), 1.17-1.20 (m, 2H), 1.32-1.45 (m, 20H), 162-168 (m, 2H), 3.04 (t, J=7.6 Hz, 2H), 3.19-3.26 (m, 1H), 3.72-3.76 (m, 1H), 7.25 (d, J=8.3 Hz, 1H), 7.75 (s, 1H), 7.82 (d, J=8.3 Hz, 1H); .sup.13C NMR (100 MHz, CDCl.sub.3) 13.9, 14.1, 22.4, 22.6, 24.9, 26.2, 26.7, 27.2, 28.3, 31.2, 31.7, 44.4, 48.4, 84.3, 118.6 (q, J=1.9 Hz), 123.8 (q, J=258 Hz), 129.8, 135.2, 136.7, 147.1 (q, J=1.9 Hz), 166.8.
(58) N,N-Dihexyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-(trifluoromethoxy)benzamide: .sup.1H NMR (400 MHz, CDCl.sub.3) 0.80 (t, J=7.2 Hz, 3H), 0.90 (t, J=6.7 Hz, 3H), 1.08-1.09 (m, 4H), 1.17-1.20 (m, 2H), 1.32-1.45 (m, 20H), 162-168 (m, 2H), 3.04 (t, J=7.6 Hz, 2H), 3.19-3.26 (m, 1H), 3.72-3.76 (m, 1H), 7.33 (d, J=7.4 Hz, 1H), 7.67 (s, 1H), 7.73 (d, J=7.4 Hz, 1H); .sup.13C NMR (100 MHz, CDCl.sub.3) 13.9, 14.1, 22.5, 22.6, 24.8, 26.2, 26.7, 27.2, 28.3, 31.3, 31.7, 44.4, 48.4, 84.4, 123.8 (q, J=258 Hz), 125.9, 127.9, 133.2, 133.3, 144.5 (q, J=1.9 Hz), 166.7.
(8)Methyl 2-(dihexylcarbamoyl)-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzoate
(59) ##STR00024##
(60) 96% yield; pale yellow oil; .sup.1H NMR (400 MHz, CDCl.sub.3) 0.79 (t, J=7.2 Hz, 3H), 0.91 (t, J=7.0 Hz, 3H), 1.05-1.07 (m, 4H), 1.15-1.20 (m, 2H), 1.30-1.47 (m, 20H), 169-172 (m, 2H), 2.99 (t, J=7.8 Hz, 2H), 3.45-3.49 (m, 2H), 3.86 (s, 3H), 7.70 (d, J=1.0 Hz, 1H), 7.83 (dd, J=8.0, 1.0 Hz, H), 7.99 (d, J=8.0 Hz, 1H); .sup.13C NMR (100 MHz, CDCl.sub.3) 13.9, 14.1, 22.3, 22.7, 24.8, 26.2, 26.9, 27.1, 28.0, 31.2, 31.7, 44.8, 48.8, 52.2, 84.3, 129.1, 129.6, 133.4, 134.5, 138.3, 166.2, 170.6; .sup.11B NMR (130 MHz, CDCl.sub.3) 29.6; IR (neat, /cm.sup.1) 2930, 2858, 1730, 1639, 1494, 1359, 1143, 964, 855, 795; HRMS (ESI.sup.+). Calcd for C.sub.27H.sub.44BNNaO.sub.3 ([M+Na].sup.+) 496.3205, Found 496.3186.
(9) N,N-Dihexyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,1-biphenyl]-2-carboxamide
(61) ##STR00025##
(62) 26% yield; colorless oil; .sup.1H NMR (400 MHz, CDCl.sub.3) 0.79 (t, J=7.2 Hz, 3H), 0.88 (t, J=7.0 Hz, 3H), 0.92-1.01 (m, 4H), 1.05-1.28 (m, 10H), 1.34 (s, 12H), 162-1.66 (m, 2H), 2.48-2.54 (m, 1H), 2.80-2.98 (m, 2H), 3.54-3.61 (m, 1H), 7.30-7.41 (m, 4H), 7.48-7.50 (m, 2H), 7.82 (s, 1H), 7.85 (dd, J=7.9, 1.1 Hz, 1H); .sup.13C NMR (100 MHz, CDCl.sub.3) 14.1, 14.2, 22.5, 22.7, 24.8, 25.1, 26.2, 26.9, 27.9, 31.2, 31.8, 44.4, 48.3, 84.0, 127.8, 128.4, 128.7, 128.9, 134.1, 135.2, 136.0, 140.0, 141.0, 171.1; .sup.11B NMR (130 MHz, CDCl.sub.3) 31.8; IR (neat, /cm.sup.1) 2928, 2857, 1629, 1466, 1387, 1318, 1144, 965, 700, 611; HRMS (ESI.sup.+) Calcd for C.sub.31H.sub.46BNNaO.sub.3 ([M+Na].sup.+) 514.3463, Found 514.3452.
(10) 2-Methyl-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-isoindolin-1-one, and 2-methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-isoindolin-1-one
(63) ##STR00026##
(64) 39% yield [meta/para=3.3]; pale yellow solid; .sup.11B NMR (130 MHz, CDCl.sub.3) 30.8; IR (neat, /cm.sup.1) 2978, 2932, 1680, 1397, 1355, 1337, 1309, 1258, 1202, 1143, 1115, 967, 863, 849, 714, 655; HRMS (ESI.sup.+) Calcd for C.sub.15H.sub.20BNNaO.sub.3 ([M+Na].sup.+) 296.1434, Found 296.1438.
(65) 2-Methyl-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-isoindolin-1-one: .sup.1H NMR (400 MHz, CDCl.sub.3) 1.35 (s, 12H), 3.18 (s, 3H), 4.36 (s, 2H), 7.41 (d, J=7.6 Hz, 1H), 7.93 (d, J=7.6 Hz, 1H), 8.29 (s, 1H); .sup.13C NMR (125 MHz, CDCl.sub.3) 24.8, 29.4, 52.1, 84.0, 121.9, 130.1, 132.3, 137.3, 143.8, 168.5.
(66) 2-Methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-isoindolin-1-one: .sup.1H NMR (400 MHz, CDCl.sub.3) 1.35 (s, 12H), 3.19 (s, 3H), 4.35 (s, 2H), 7.81 (d, J=7.6 Hz, 1H), 7.86 (s, 1H), 7.89 (d, J=7.6 Hz, 1H); .sup.13C NMR (125 MHz, CDCl.sub.3) 24.9, 29.5, 52.9, 84.2, 122.7, 128.7, 134.3, 135.2, 140.1, 168.6.
(11) N,N-Dimethyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide and N,N-dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide
(67) ##STR00027##
(68) 41% yield [meta/para=13]; white solid; .sup.11B NMR (130 MHz, CDCl.sub.3) 30.6; IR (neat, /cm.sup.1) 2978, 1634, 1482, 1356, 1267, 1213, 965, 812, 709, 671; HRMS (ESI.sup.+) Calcd for C.sub.15H.sub.22BNNaO.sub.3 ([M+Na].sup.+) 298.1585, Found 298.1585.
(69) N,N-Dimethyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide: .sup.1H NMR (500 MHz, CDCl.sub.3) 1.34 (s, 12H), 2.96 (s, 3H), 3.10 (s, 3H), 7.40 (dd, J=8.0, 8.0 Hz, 1H), 7.49 (ddd, J=8.1, 1.1, 1.1 Hz, 1H), 7.82-7.84 (m, 2H); .sup.13C NMR (100 MHz, CDCl.sub.3) 25.0, 35.4, 39.7, 84.1, 127.9, 129.8, 133.2, 135.8, 135.9, 171.8.
(70) N,N-Dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide: .sup.1H NMR (400 MHz, CDCl.sub.3) 1.35 (s, 12H), 3.19 (s, 3H), 4.35 (s, 2H), 7.81 (d, J=7.6, Hz, 1H), 7.86 (s, 1H), 7.89 (d, J=7.6 Hz, 1H); .sup.13C NMR (125 MHz, CDCl.sub.3) 24.9, 29.5, 51.9, 84.2, 122.7, 128.7, 134.3, 135.2, 140.1, 168.6.
N,N-Dimethyl-3,5-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide
(71) ##STR00028##
(72) 11% yield; white solid; .sup.1H NMR (400 MHz, CDCl.sub.3) 1.33 (s, 24H), 2.95 (s, 3H), 3.09 (s, 3H), 7.93 (d, J=1.3 Hz, 2H), 8.28 (t, J=1.3 Hz, 1H); .sup.13C NMR (100 MHz, CDCl.sub.3) 25.0, 35.3, 39.8, 84.1, 135.5, 135.9, 142.1, 171.9; .sup.11B NMR (130 MHz, CDCl.sub.3) 30.6; IR (neat, /cm.sup.1) 2978, 1636, 1594, 1380, 1330, 1213, 1142, 889, 755, 689; HRMS (ESI.sup.+) Calcd for C.sub.21H.sub.33B.sub.2NNaO.sub.3 ([M+Na].sup.+) 424.2437, Found 424.2455.
(12) 1-Piperidinyl(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)methanone
(73) ##STR00029##
(74) 50% yield; white solid; .sup.1H HMR (400 MHz, CDCl.sub.3) 1.34 (s, 1.2H), 1.48-1.51 (m, 2H), 1.63-1.70 (m, 4H), 3.29-3.37 (m, 2H), 3.67-3.73 (m, 2H), 7.38 (dd, J=7.6, 6.7 Hz, 1H), 7.46 (d, J=7.6 Hz, 1H), 7.81-7.82 (m, 2H); .sup.13C NMR (100 MHz, CDCl.sub.3) 24.7, 25.0, 25.7, 26.6, 43.1, 48.9, 84.1, 127.8, 129.5, 133.1, 135.7, 136.1, 170.4; .sup.11B NMR (130 MHz, CDCl.sub.3) 30.8; IR (neat, /cm.sup.1) 2938, 1714, 1626, 1358, 1271, 1143, 1094, 964, 859, 754, 666; HRMS (ESI.sup.+) Calcd for C.sub.18H.sub.26BNNaO.sub.3 ([M+Na].sup.+) 338.1898, Found 338.1897.
1-Piperidinyl(3,5-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)methanone
(75) ##STR00030##
(76) 11% yield; white solid; .sup.1H NMR (400 MHz, CDCl.sub.3) 1.37 (s, 24H), 1.49-1.65 (m, 6H), 3.32-3.33 (m, 2H), 3.64-3.70 (m, 2H), 7.89 (s, 2H), 8.27 (s, 1H); .sup.13C NMR (100 MHz, CDCl.sub.3) 24.7, 25.0, 25.7, 26.6, 43.1, 48.9, 84.1, 135.6, 135.8, 142.1, 170.5; .sup.11NMR (130 MHz, CDCl.sub.3) 30.8; IR (neat, /cm.sup.1) 2979, 1624, 1329, 1267, 1142, 966, 889, 755, 716, 666; HRMS (ESI.sup.+) Calcd for C.sub.24H.sub.37B.sub.2NNaO.sub.5 ([M+Na].sup.+) 464.2750, Found 464.2728.
(13) (2-Bromo-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-4-morpholinylmethanone and (2-bromo-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-4-morpholinylmethanone
(77) ##STR00031##
(78) 88% yield [meta/para=3.2]; pale yellow solid; .sup.11B NMR (130 MHz, CDCl.sub.3) 30.8; IR (KBr, /cm.sup.1) 2977, 2927, 2857, 1645, 1592, 1434, 1386, 1356, 1280, 1248, 1143, 1114, 1094, 1016, 848, 689; HRMS (ESI.sup.+) Calcd for C.sub.17H.sub.23BBrNNaO.sub.4 ([M+Na].sup.+) 418.0801, Found 418.0791
(79) (2-Bromo-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-4-morpholinylmethanone: .sup.1H NMR (500 MHz, CDCl.sub.3) 1.30 (s, 12H), 3.10-3.29 (m, 2H), 3.50-3.61 (m, 1H), 3.64-3.80 (m, 4H), 3.80-3.89 (m, 1H), 7.55 (d, J=8.0 Hz, 1H), 7.62 (dd, J=8.0, 1.8 Hz, 1H), 7.65 (d, J=1.8 Hz, 1H); .sup.13C NMR (125 MHz, CDCl.sub.3) 24.9, 41.8, 47.0, 66.5, 66.6, 84.2, 122.4, 132.0, 133.8, 136.4, 138.7, 167.7.
(80) (2-Bromo-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-4-morpholinylmethanone: .sup.1H NMR (500 MHz, CDCl.sub.3) 1.28 (s, 12H), 3.10-3.29 (m, 2H), 3.50-3.61 (m, 1H), 3.64-3.80 (m, 4H), 3.80-3.89 (m, 1H), 7.22 (d, J=7.5 Hz, 1H), 7.74 (d, J=7.5 Hz, 1H), 7.97 (s, 1H); .sup.13C NMR (125 MHz, CDCl.sub.3) 24.5, 41.8, 47.0, 66.5, 66.6, 84.3, 118.8, 127.0, 133.8, 136.9, 139.8, 167.5.
(14) Azepane-1-yl(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl) methanone
(81) ##STR00032##
(82) 36% yield; white solid; .sup.1H NMR (400 MHz, CDCl.sub.3) 1.34 (s, 12H), 1.59-1.64 (m, 6H), 1.81-1.85 (m, 2H), 3.36 (t, J=5.4 Hz, 2H), 3.67 (t, J=5.8, Hz, 2H), 7.38 (dd, J=7.9, 7.6 Hz, 1H); 7.46 (d, J=7.9 Hz, 1H), 7.80-7.82 (m, 2H); .sup.13C NMR (100 MHz, CDCl.sub.3) 25.0, 26.6, 27.4, 28.0, 29.6, 46.3, 49.9, 84.1, 127.8, 129.2, 132.8, 135.4, 136.9, 171.7; .sup.11B NMR (130 MHz, CDCl.sub.3) 30.6; IR (neat, /cm.sup.1) 2977, 2928, 1631, 1409, 1356, 1319, 1216, 1099, 859, 708; HRMS (ESI.sup.+) Calcd for C.sub.13H.sub.28BNNaO.sub.3 ([M+H].sup.+) 352.2054, Found 352.2049.
Azepane-1-yl(3,5-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)methanone
(83) ##STR00033##
(84) 12% yield; white solid; .sup.1H NMR (400 MHz, CDCl.sub.3) 1.33 (s, 24H), 1.58-1.59 (m, 6H), 1.80-1.86 (m, 2H), 3.36 (t, J=5.4 Hz, 2H), 3.65 (t, J=5.4 Hz, 2H), 7.90 (s, 2H), 8.27 (s, 1H); .sup.13C NMR (1.00 MHz, CDCl.sub.3) 25.0, 26.7, 27.5, 28.1, 29.6, 46.1, 50.0, 84.1, 135.5, 136.3, 141.8, 171.8; .sup.11B NMR (130 MHz, CDCl.sub.3) 31.3; IR (neat, /cm.sup.) 2930, 2927, 1628, 1429, 1389, 1270, 1142, 889, 754, 689; HRMS (ESI.sup.+) Calcd for C.sub.25H.sub.39B.sub.2NNaO.sub.5 ([M+Na].sup.+) 478.2907, Found 478.2926.
N,N-Dihexyl-2-(trifluoromethyl)-5-(4,4,6-trimethyl-1,3,2-dioxaborolan-2-yl)benzamide and N,N-dihexyl-2-(trifluromethyl)-4-(4,4,6-trimethyl-1,3,2-dioxaborolan-2-yl)benzamide
(85) ##STR00034##
(86) 62% yield, [meta/para=5.3]; colorless oil; .sup.11B NMR (130 MHz, CDCl.sub.3) 26.2; IR (neat, /cm.sup.1) 2931, 1644, 1502, 1408, 1306, 1170, 1033, 844, 767, 687; HRMS (ESI.sup.+) Calcd for C.sub.25H.sub.41BF.sub.5NHaO.sub.3 ([M+Na].sup.+) 506.3024, Found 506.3013.
(87) N,N-Dihexyl-2-(trifluoromethyl)-5-(4,6-trimethyl-1,3,2-dioxaborolan-2-yl)benzamide: .sup.1H NMR (500 MHz, CDCl.sub.3) 0.81, (t, J=7.2 Hz, 3H), 0.89-0.92 (m, 3H), 1.08-1.09 (m, 4H), 1.17-1.21 (m, 2H), 1.33-1.47 (m, 18H), 1.61-1.64 (m, 2H), 1.86-1.91 (m, 1H), 2.95-3.00 (m, 2H), 3.12-3.19 (m, 1), 3.77-3.84 (m, 1H), 4.13-4.37 (m, 1H), 7.60 (d, J=7.6 Hz, 1H), 7.75 (s, 1H), 7.87 (d, J=7.6 Hz, 1H); .sup.13C NMR (100 MHz, CDCl.sub.3) 14.0, 14.1, 22.5, 22.7, 23.1, 26.2, 26.4, 26.9, 28.0, 28.2, 31.2, 31.4, 31.7, 44.4, 46.0, 48.7, 65.4, 71.6, 124.0 (q, J=274 Hz), 125.2 (q, J=3.6 Hz), 126.4, 127.6 (q, J=32.3 Hz), 132.9, 133.9, 169.2; .sup.19F NMR (368 MHz, CDCl.sub.3) 61.9.
(88) N,N-Dihexyl-2-(trifluoromethyl)-4-(4,4,6-trimethyl-1,3,2-dioxaborolan-2-yl)benzamide: .sup.1H NMR (500 M Hz, CDCl.sub.3) 0.81 (t, J=7.2 Hz, 3H), 0.89-0.92 (m, 3H), 1.08-1.09 (m, 4H), 1.17-1.21 (m, 2H), 1.33-1.47 (m, 18H), 1.61-1.64 (m, 2H), 1.86-1.91 (m, 1H), 2.95-3.00 (m, 2H), 3.12-3.19 (m, 1H), 3.77-3.84 (m, 1H), 4.13-4.37 (m, 1H), 7.26 (d, J=6.7 Hz, 1H), 7.96 (d, J=6.7 Hz, 1H), 8.08 (s, 1H); .sup.13C NMR (100 MHz, CDCl.sub.3) 14.0, 14.1, 22.4, 22.7, 23.1, 26.2, 26.4, 26.9, 28.0, 28.2, 31.2, 31.3, 31.7, 44.4, 46.0, 48.7, 65.4, 71.6, 124.3 (q, J=296 Hz), 125.7, 127.6 (q, J=32.3 Hz), 131.8 (q, J=4.8 Hz), 134.6, 169.2; .sup.19F NMR (368 MHz, CDCl.sub.3) 61.5.
(16) 3-Fluoro-N,N-dihexyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide and 3-fluoro-N,N-dihexyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide
(89) ##STR00035##
(90) 99% yield [meta/para=7.7]; colorless oil; .sup.11B NMR (130 MHz, CDCl.sub.3) 30.0; IR, (neat, /cm.sup.1) 2929, 1633, 1368, 1143, 1099, 968, 923, 854, 756, 676; HRMS (ESI.sup.) Calcd for C.sub.25H.sub.41BFNNaO.sub.3 ([M+Na].sup.+) 456.3056, Found 456.3035.
(91) 3-Fluoro-N,N-dihexyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide: .sup.1H NMR (400 MHz, CDCl.sub.3) 0.82 (t, J=8.7 Hz, 3H), 0.89-0.91 (m, 3H), 1.12-1.17 (m, 4H), 1.21-1.49 (m, 22H), 1.61-1.62 (m, 2H), 3.14 (t, J=7.2 Hz, 2H), 3.44 (t, J=7.2 Hz, 2H), 7.13 (d, J=8.8 Hz, 1H), 7.48 (d, J=8.8 Hz, 1H), 7.55 (s, 1H); .sup.13C NMR (100 MHz, CDCl.sub.3) 14.0, 14.1, 22.5, 22.7, 24.9, 26.2, 26.8, 27.5, 28.7, 31.3, 31.7, 45.0, 49.1, 84.3, 116.5 (d, J=22.6 Hz) 121.6 (d, J=19.7 Hz), 128.2 (d, J=2.8 Hz), 138.9 (d, J=6.6 Hz), 162.2 (d, J=248 Hz), 170.1; .sup.19F NMR (368 MHz, CDCl.sub.3) 115.3 (s, 1F).
(92) 3-Fluoro-N,N-dihexyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide: .sup.1H NMR (400 MHz, CDCl.sub.3) 0.82 (t, J=6.7 Hz, 3H), 0.89-0.91 (m, 3H), 1.12-1.18 (m, 4H), 1.21-1.49 (m, 22H), 1.61-1.62 (m, 2H), 3.14 (t, J=7.2 Hz, 2H), 3.44 (t, J=7.2 Hz, 2H), 7.01 (d, J=9.0 Hz, 1H), 7.11 (d, J=9.0 Hz, 1H), 7.73-7.77 (m, 1H); .sup.13C NMR (100 MHz, CDCl.sub.3) 14.0, 14.1, 22.5, 22.7, 24.9, 26.2, 26.8, 27.5, 28.7, 31.3, 31.7, 44.8, 49.0, 84.2, 113.6 (d, J=26.3 Hz), 132.0 (br), 137.1 (d, J=8.4 Hz), 142.4 (d, J=7.5 Hz), 165.4 (d, J=253 Hz), 169.9; .sup.19F NMR (368 MHz, CDCl.sub.3) 103.7 (s, 1F).
(17) 3-Bromo-N,N-dihexyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide
(93) ##STR00036##
(94) 86% yield; pale yellow oil; .sup.1H NMR (400 MHz, CDCl.sub.3) 0.83 (t, J=7.2 Hz, 3H), 0.89-0.91 (m, 3H), 1.12-1.17 (m, 4H), 1.21-1.33 (m, 20H), 1.49-1.63 (m, 4H), 3.13 (t, J=7.6 Hz, 2H), 3.43 (t, J=7.6 Hz, 2H), 7.56 (s, 1H), 7.69 (s, 1H), 7.93 (s, 1H); .sup.13C NMR (100 MHz, CDCl.sub.3) 14.0, 14.1, 22.5, 22.7, 24.9, 26.2, 26.8, 27.5, 28.7, 31.3, 31.7, 45.0, 49.1, 84.4, 122.4, 131.0, 132.1, 138.0, 138.8, 169.9; .sup.11B NMR (130 MHz, CDCl.sub.3) 30.7; IR (neat, /cm.sup.1) 2929, 2857, 1635, 1435, 1348, 1143, 965, 964, 885, 704; HRMS (ESI.sup.+) Calcd for C.sub.25H.sub.41BBrNNaO.sub.3 ([M+N].sup.+) 516.2255, Found 516.2255.
(18) N,N-Dihexyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2yl)-[1,1-biphenyl]-3-carboxamide
(95) ##STR00037##
(96) 81% yield; pale yellow oil; .sup.1H NMR (400 MHz, CDCl.sub.3) 0.79 (t, J=7.2 Hz, 3H), 0.90-0.92 (m, 3H), 1.11-1.19 (m, 6H), 1.23-1.35 (m, 18H), 1.51-1.53 (m, 2H), 1.63-1.66 (m, 2H), 3.20 (t, J=7.6 Hz, 2H), 3.48 (t, J=8.1 Hz, 2H), 7.34 (t, J=7.4 Hz, 1H), 7.43 (dd, J=8.1, 7.4 Hz, 2H), 7.62 (d, J=8.1 Hz, 2H), 7.66 (s, 1H), 7.76 (s, 1H), 8.05 (s, 1H); .sup.13C NMR (100 MHz, CDCl.sub.3) 14.1, 14.2, 22.5, 22.8, 25.0, 26.3, 27.0, 27.7, 28.9, 31.4, 31.8, 45.0, 49.3, 84.2, 127.3, 127.6, 128.0, 128.8, 131.6, 134.1, 137.5, 140.6, 140.8, 171.6; .sup.11B NMR (130 MHz, CDCl.sub.3) 32.5; IR (neat, /cm.sup.1) 2929, 2857, 1634, 1411, 1321, 1144, 966, 894, 756, 698; HRMS (ESI.sup.+) Calcd for C.sub.32H.sub.46BNNaO.sub.3 ([M+N].sup.+) 514.3463, Found 514.3456.
(19) 3-Cyano-N,N-dihexyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2yl)benzamide
(97) ##STR00038##
(98) 87% yield; pale yellow oil; .sup.1H HMR (400 MHz, CDCl.sub.3) 0.82 (t, J=7.2 Hz, 3H), 0.88-0.90 (m, 3H), 1.11-1.42 (m, 24H), 1.48-1.52 (m, 2H), 1.65-1.69 (m, 2H), 3.11 (t, J=7.6 Hz, 2H) 3.43 (t, J=7.6 Hz, 2H), 7.69 (dd, J=1.6, 1.6 Hz, 1H), 7.97 (dd, J=1.6, 1.4 Hz, 1H), 8.08 (dd, J=1.6, 1.4 Hz, 1H); .sup.13C NRM (100 MHz, CDCl.sub.3) 14.0, 14.1, 22.4, 22.6, 24.9, 26.2, 26.8, 27.5, 28.7, 31.2, 31.6, 45.1, 49.2, 84.8, 112.4, 118.2, 132.3, 136.6, 137.9, 138.7, 169.2; .sup.11B NMR (130 MHz, CDCl.sub.3) 30.3; IR (neat, /cm.sup.l) 2930, 2857, 2231, 1637, 1371, 1265, 1143, 966, 850, 704; HRMS (ESI.sup.+) Calcd for C.sub.26H.sub.41BN.sub.2NaO.sub.3 ([M+Na].sup.+) 463.3102, Found 463.3124.
(20) 2,3-Dichloro-N,N-dihexyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide
(99) ##STR00039##
(100) 94% yield; pale yellow oil; .sup.1H HMR (500 MHz, CDCl.sub.3) 0.81 (t, J=7.5 Hz, 3H), 0.91 (t, J=6.7 Hz, 3H), 1.08-1.11 (m, 4H), 1.18-1.21 (m, 2H), 1.32-1.50 (m, 20H), 1.65-1.70 (m, 2H), 2.98-3.02 (m, 1H), 3.05-3.09 (m, 1H), 3.26-3.31 (m, 1H), 3.64-3.70 (m, 1H), 7.56 (d, J=1.2 Hz, 1H), 7.85 (d, J=1.2 Hz, 1H); .sup.13C NRM (100 MHz, CDCl.sub.3) 14.0, 14.1, 22.4, 22.7, 24.9 (br), 26.2, 26.8, 27.3, 28.3, 31.2, 31.7, 44.7, 48.5, 84.6, 131.6, 131.9, 133.1, 136.3, 138.4, 167.3; .sup.11B NMR (130 MHz, CDCl.sub.3) 30.4; IR (neat, /cm.sup.1) 2930, 2858, 1644, 1467, 1350, 1268, 1142, 965, 894, 755; HRMS (ESI.sup.+) Calcd for C.sub.25H.sub.40BCl.sub.2NNaO.sub.3 ([M+Na].sup.+) 506.2371, Found 506.2394.
(21) 2-Fluoro-N,N-dihexyl-5-(4,4,5,5-tetraamethyl-1,3,2-dioxaborolan-2-yl)-3-(trifluoromethyl)benzamide
(101) ##STR00040##
(102) 89% yield; pale yellow oil; .sup.1NMR (400 MHz, CDCl.sub.3) 0.80 (t, J=7.2 Hz, 3H), 0.90 (t, J=6.7 Hz, 3H), 1.08-1.11 (m, 4H), 1.17-1.22 (m, 2H), 1.33-1.49 (m, 20H), 1.65-1.67 (m, 2H), 3.14 (t, J=7.6 Hz, 2H), 3.40-3.64 (m, 2H), 7.94 (d, J=6.3 Hz, 1H), 8.05 (d, J=7.2 Hz, 1H); .sup.13C NMR (100 MHz, CDCl.sub.3) 13.9, 14.1, 22.4, 22.6, 24.9, 26.1, 26.7, 27.4, 28.4, 31.2, 31.7, 44.9, 48.8, 84.7, 118.4 (qd, J=33.6, 12.0 Hz), 122.5 (q, J=272 Hz), 126.6 (d, J=18.0 Hz), 134.1 (d, J=3.6 Hz), 139.2 (d, J=4.8 Hz), 157.3 (d, J=260 Hz), 165.0; .sup.19F NMR (368 MHZ, CDCl.sub.3) 115.4 (s, 1F), 63.1 (s, 3F); .sup.11B NMR (130 MHz, CDCl.sub.3) 30.1; IR (neat, /cm.sup.1) 2931, 1644, 1468, 1385, 1302, 1239, 1197, 914, 756, 672; HRMS (ESI.sup.+) Calcd for C.sub.26H.sub.46BF.sub.4NNaO.sub.3 ([M+Na].sup.+) 524.2930, Found 524.2939.
(22) N,N-Dihexyl-2-(5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophene) carboxamide
(103) ##STR00041##
(104) 51% yield; pale yellow oil; .sup.1H NMR (500 MHz, CDCl.sub.3) 0.80-0.92 (m, 6H), 1.16-1.38 (m, 12H), 1.33 (s, 12H), 1.53-1.70 (m, 4H), 3.38-3.44 (m, 4H), 7.30 (d, J=3.6 Hz, 1H), 7.50 (d, J=3.6 Hz, 1H); .sup.13C NMR (125 MHz, CDCl.sub.3) 13.9 (2C), 22.5, 24.7 (2C), 26.4 (br, 2C), 27.5 (br), 28.8 (br), 31.4 (2C), 46.1 (br), 49.3 (br), 84.3, 129.1, 136.3, 144.2, 164.3; .sup.11B NMR (130 MHz, CDCl.sub.3) 29.0; IR (neat, /cm.sup.1) 2956, 2929, 2862, 1625, 1525, 1463, 1419, 1372, 1350, 1287, 1270, 1210, 1143, 1063, 1021, 997, 857, 853, 820, 739, 687, 667; HRMS (ESI.sup.+) Calcd for C.sub.23H.sub.40BNNaO.sub.3S ([M+Na].sup.+) 444.2720, Found 444.2731.
N,N-Dihexyl-2-(3,5-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophene) carboxamide
(105) ##STR00042##
(106) 14% yield; pale brown oil; .sup.1H NMR (500 MHz, CDCl.sub.3) 0.75-0.96 (m, 6H), 1.03-1.53 (m, 40H), 3.05-3.22 (m, 2H), 3.35-3.55 (m, 2H), 7.83 (s, 1H); .sup.13C NMR (125 MHz, CDCl.sub.3) 13.97, 14.03, 22.4, 22.6, 24.7, 24.8, 26.2, 26.9, 27.0, 28.3, 31.3, 31.7, 45.2, 49.0, 83.6, 84.2, 143.1, 153.2, 165.5; .sup.11B NMR (130 MHz, CDCl.sub.3) 28.6; 1H (neat, /cm.sup.1) 3424, 2929, 2859, 1633, 1536, 1455, 1371, 1321, 1268, 1213, 1139, 1111, 1028, 1002, 967, 911, 882, 851, 829, 727, 688, 666; HRMS (ESI.sup.+) Calcd for C.sub.29H.sub.51B.sub.2NNaO.sub.5S ([M+Na].sup.+) 570.3572, Found 570.3551.
(23) N,N-Dihexyl-5-(4,4,5,5-tetramethyl, 1,3,2-dioxaborolan-2-yl)-pyrrole-2-carboxamide
(107) ##STR00043##
(108) 79% yield; colorless oil; .sup.1H NMR (400 MHz, CDCl.sub.3) 0.81-0.93 (m, 6H), 1.23-1.36 (m, 24H), 1.53-1.78 (m, 4H), 3.25-3.70 (m, 4H), 6.43-6.70 (m, 1H), 6.74-6.78 (m, 1H), 9.85 (brs, 1H); .sup.13C NMR (125 MHz, CDCl.sub.3) 14.0 (2C), 22.5, 24.7 (2C), 26.6 (2C), 27.6 (br), 28.8 (br), 31.5 (2C), 47.2 (br), 48.5 (br), 83.8, 111.6, 120.2, 129.2, 161.5; .sup.11B NMR (130 MHz, CDCl.sub.3) 28.3; IR (neat, /cm.sup.1) 3441, 3256, 2929, 2858, 1610, 1553, 1467, 1424, 1345, 1300, 1265, 1219, 1144, 973, 855, 790, 759, 704; HRMS (ESI.sup.+) Calcd for C.sub.23H.sub.41BN.sub.2NaO.sub.3 ([M+Na].sup.+) 427.3108, Found 427.3114.
(24) N,N-Dihexyl-(1-methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrrole)-2-carboxamide and N,N-dihexyl-(1-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrrole)-2-carboxamide
(109) ##STR00044##
(110) 74% yield [5-/4-=6.7]; pale yellow oil; .sup.11B NMR (130 MHz, CDCl.sub.3) 28.3; IR (neat, /cm.sup.1) 2929, 2858, 1628, 1531, 1467, 1416, 1373, 1302, 1265, 1145, 1108, 1091, 965, 858, 754, 692; HRMS (ESI.sup.+) Calcd for C.sub.24H.sub.43BN.sub.2NaO.sub.3 ([M+Na].sup.+) 441.3264, Found 441.3255.
(111) N,N-Dihexyl-(1-methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrrole)-2-carboxamide: .sup.1H NMR (500 MHz, CDCl.sub.3) 0.78-0.94 (m, 6H), 1.10-1.40 (m, 24H), 1.42-1.75 (m, 4H), 3.26-3.54 (m, 4H), 3.82 (s, 3H), 6.20 (d, J=4.0 Hz, 1H), 6.70 (d, J=4.0 Hz, 1H); .sup.13C NMR (125 MHz, CDCl.sub.3) 13.9 (2C), 22.5 (2C), 24.7, 26.4 (br, 2C), 27.5 (br), 28.6 (br), 31.4 (2C), 34.6, 44.6 (br), 48.9 (br), 83.2, 109.7, 120.2, 132.5, 164.5.
(112) N,N-Dihexyl-(1-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrrole)-2-carboxamide: .sup.1H NMR (500 MHz, CDCl.sub.3) 0.78-0.94 (m, 6H), 1.10-1.40 (m, 24H), 1.42-1.75 (m, 4H), 3.26-3.54 (m, 4H), 3.71 (s, 3H), 6.56-6.60 (m, 1H), 7.04-7.11 (m, 1H); .sup.13C NMR, (125 MHz, CDCl.sub.3) 13.9 (2C), 22.5 (2C), 24.7, 26.4 (2C), 27.5 (br), 28.6 (br), 31.4 (2C), 35.6, 44.6 (br), 48.9 (br), 82.9, 117.0, 127.6, 134.0, 164.0.
(25) N,N-Dihexyl-(7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole)-2-carboxamide
(113) ##STR00045##
(114) 71% yield; pale yellow oil; .sup.1H NMR (500 MHz, CDCl.sub.3) 0.87-0.96 (m, 6H), 1.30-1.41 (m, 12H), 1.39 (s, 12H), 1.60-1.85 (m, 4H), 3.30-3.90 (m, 4H), 6.75 (d, J=2.3 Hz, 1H), 7.15 (t, J=8.0 Hz, 1H), 7.75 (d, J=8.0 Hz, 1H), 7.78 (d, J=8.0 Hz, 1H), 9.94 (brs, 1H); .sup.13C NMR (125 MHz, CDCl.sub.3) 14.0 (2C), 22.5 (2C), 24.9, 26.6 (br, 2C), 27.6 (br), 28.8 (br), 31.5 (2C), 47.4 (br), 49.0 (br), 83.9, 103.9, 119.9, 125.3, 126.9, 129.9, 131.7, 140.0, 162.5; .sup.11B NMR (130 MHz, CDCl.sub.3) 31.2; IR (neat, /cm.sup.1) 3438, 3056, 2927, 2857, 1615, 1595, 1529, 1463, 1443, 1369, 1288, 1200, 1146, 1130, 1110, 1045, 979, 849, 813, 748, 734, 678; HRMS (ESI.sup.+) Calcd for C.sub.27H.sub.43BN.sub.2NaO.sub.3 ([M+Na].sup.+) 477.3264 Found 477.3264.
(26) N,N-Dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) picolinamide and N,N-dimethyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2yl) picolinamide
(115) ##STR00046##
(116) 43% yield [4-/5=3.6]; white solid; .sup.13C NMR (100 MHz, CDCl.sub.3) (4- and 5-position isomers) 25.0 (4- and 5-position isomers), 35.71, 35.76, 39.0, 39.1, 84.6, 84.8, 122.7, 128.5, 129.3, 143.4, 147.9, 154.07, 154.13, 156.5, 169.4 (4- and 5-position isomers); .sup.11B NMR (130 MHz, CDCl.sub.3) 30.6; IR (neat, /cm.sup.1) 2979, 1640, 1473, 1358, 1263, 1105, 965, 857, 752, 672; HRMS (ESI.sup.+) Calcd for C.sub.14H.sub.21BN.sub.2NaO.sub.3 ([M+Na].sup.+) 299.1537, Found 299.1534.
(117) N,N-Dimethyl-4-(4,4,5,5-tetraramethyl-1,3,2-dioxaborolan-2yl) picolinamide: .sup.1H NMR (500 MHz, CDCl.sub.3) 1.34 (s, 12H), 3.04 (s, 3H), 3.13 (s, 3H), 7.65 (d, J=5.8 Hz, 1H), 7.96 (s, 1H), 8.60 (d, J=5.8 Hz, 1H).
(118) N,N-Dimethyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaboralan-2-yl) picolinamide: .sup.1H NMR (500 MHz, CDCl.sub.3) 1.36 (s, 12H), 3.04 (s, 3H), 3.13 (s, 3H), 7.58 (d, J=7.8 Hz, 1H), 8.15 (d, J=7.8 Hz, 1H), 8.91 (s, 1H).
(119) As can be seen from the above-described results, the borylation of aromatic compounds by the catalyst of the present invention results in the meta-selective borylation.
(120) (27) Table 1 shows the meta-para selectivity (m/p) in the case where the borylation reaction was performed in the same manner as Example 9(1) by using the ligands described in Examples 2 to 6.
(121) TABLE-US-00001 TABLE 1 R.sup.2 X m/p n-Hex m/p = 7.4
Example 10
(122) (1) The borylation reaction was performed by using alkoxycarbonyl-substituted pyridines and alkoxycarbonylmethyl-substituted pyridines as the substituted aromatic compounds, the substrates of the borylation reaction, in the same manner as: Example 9 (1).
(123) In a dried test tube, to a p-xylene (1.5 mL) solution of an alkoxycarbonyl-substituted pyridine (1.00 equiv), [Ir(OMe) (cod)].sub.2 (1.5 mol %), 1-(2-([2,2-bipyridin]-5-yl)phenyl)-3-(4-triflioromethylphenyl) urea (3.0 mol %) and bis(pinacolato)diboron (1.5 equiv) were added and stirred at 25 C. for 18 hours. The solvent was removed under reduced pressure, and then the products were isolated and prepared by recycling preparative HPLC.
(124) ##STR00051##
(125) The obtained compounds were as follows.
Ethyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine-2-carboxylate and ethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine-2-carboxylate
(126) ##STR00052##
(127) 70% yield [5-/4-=5.0]; white solid; .sup.13C NMR (100 MHz, CDCl.sub.3) (4- and 5-position isomers) 25.0 (4- and 5-position isomers), 35.71, 35.76, 39.0, 39.1, 84.6, 84.8, 122.7, 128.5, 129.3, 143.4, 147.9, 154.07, 154.13, 156.5, 169.4 (4- and 5-position isomers); .sup.11B NMR (130 MHz, CDCl.sub.3) 30.6; IR (neat, /cm.sup.1) 2979, 1640, 1473, 1358, 1263, 1105, 965, 857, 752, 672; HRMS (ESI.sup.+) Calcd for C.sub.14H.sub.21BN.sub.2NaO.sub.3 ([M+Na].sup.+) 299.1537, Found 299.1534.
(128) Ethyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine-2-carboxylate: .sup.1H NMR (500 MHz, CDCl.sub.3) 1.36 (s, 12H), 3.04 (s, 3H), 3.13 (s, 3H), 7.58 (d, J=7.8 Hz, 1H), 8.15 (d, J=7.6 Hz, 1H), 8.91 (s, 1H).
(129) Ethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine-2-carboxylate; .sup.1H NMR (500 MHz, CDCl.sub.3) 1.34 (s, 12H), 3.04 (s, 3H), 3.13 (s, 3H), 7.65 (d, J=5.8 Hz, 1H), 7.96 (s, 1H), 8.60 (d, J=5.8 Hz, 1H).
(130) By using the ligand used in (1), the following compounds were obtained in the same manner as the method of (1).
(2) 2-Ethoxycarbonylmethyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine and 2-ethoxycarbonylmethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine
(131) ##STR00053##
(132) 64% yield [5-/4-=1.7]; pale brown oil; .sup.11B NMR (130 MHz, CDCl.sub.3) 30.9; IR (neat, /cm.sup.1) 2980, 2934, 1739, 1600, 1557, 1480, 1403, 1371, 1258, 1166, 1145, 1099, 1028, 964, 856, 668; HRMS (ESI.sup.+) Calcd for C.sub.15H.sub.22BNNaO.sub.4 ([M+Na].sup.+) 314.1540, Found 314.1539.
(133) 2-Ethoxycarbonylmethyl-5-(4,4,5,5-tetramethyl-1,3,2dioxaborolan-2-yl)pyridine: .sup.1H NMR (500 MHz, CDCl.sub.3) 1.18-1.25 (m, 3H), 1.32 (s, 12H), 3.83 (s, 2H), 4.10-4.20 (m, 2H), 7.26 (d, J=8.0 Hz, 1H), 8.00 (d, J=8.0 Hz, 1H), 8.86 (s, 1H); NMR (100 MHz, CDCl.sub.3) 14.1, 24.7, 44.1, 61.0, 84.1, 123.1, 142.9, 155.2, 156.8, 170.4.
(134) 2-Ethoxycarbonylmethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine; .sup.1H NMR (500 MHz, CDCl.sub.3) 1.18-1.25 (m, 3H), 1.32 (s, 12H), 3.82 (s, 2H), 4.10-4.20 (m, 2H), 7.50 (d, J=4.6 Hz, 1H), 7.60 (s, 1H), 8.56 (d, J=4.6 Hz, 1H); .sup.13C NMR (100 MHz, CDCl.sub.3) 14.1, 24.8, 43.8, 60.9, 84.4, 127.0, 128.9, 148.9, 153.8, 170.7.
Example 11
(135) (1) The borylation reaction was performed by using a phosphate-, phosphinediamide- or phosphine oxide-substituted benzene as the substituted aromatic compound, the substrate of the borylation reaction, in the same manner as Example 9.
(136) In a dried test tube, to a p-xylene (1.5 mL) solution of a phosphate-, phosphinediamide- or phosphine oxide-substituted benzene (1.00 equiv), [Ir(OMe) (cod)].sub.2 (1.5 mol %), 1-(2-([2,2-bipyridin]-5-yl)phenyl)-3-cyclohexylurea (3.0 mol %) and bis(pinacolato)diboron (1.5 equiv) were added and stirred at 25 C. or 40 C. for 16 hours. The solvent was removed under reduced pressure, and then the products were isolated and prepared by recycling preparative HPLC.
(137) ##STR00054##
(wherein R represents an ethoxy group, a diethylamino group or a cyclohexyl group (abbreviated as Cy), and Y represents H, Br, Cl, CF.sub.3, CMe or Me).
(138) The obtained compounds were as follows.
3-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)phenyldiethylphosphonate and 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyldiethylphosphonate
(139) ##STR00055##
(140) 41% yield, [meta/para=17]; colorless solid; .sup.11B NMR (130 MHz, CDCl3) 30.7; .sup.31P NMR (158 MHz, CDCl.sub.3) 28.5, 28.1; IR (KBr, /cm.sup.1) 2980, 1599, 1481, 1408, 1390, 1358, 1324, 1243, 1211, 1133, 1136, 1097, 1055, 1027, 965, 969, 843, 795, 767, 704, 669; HRMS (ESI.sup.+) Calcd for C.sub.16H.sub.26BO.sub.5P ([M+Na].sup.+) 363.1509, Found 363.1498.
(141) 3-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)phenyldiethylphosphonate: .sup.1H NMR (400 MHz, CDCl.sub.3) 1.30 (b, J=7.2 Hz, 6H), 1.32 (s, 12H), 3.98-4.18 (m, 4H), 7.44 (ddd, J=7.6, 7.6, 4.0 Hz, 1H), 7.88 (ddd, J=13.0, 7.6, 1.3 Hz, 1H), 7.95 (dd, J=7.6, 1.3 Hz, 1H), 8.24 (d, J=13.0 Hz, 1H), .sup.13C NMR, (100 MHz, CDCl.sub.3) 16.3 (d, J.sub.C-P=6.6 Hz), 24.8, 62.0 (d, J.sub.C-P=5.8 Hz), 84.0, 127.6 (d, J.sub.C-P=187 Hz), 127.7 (d, J.sub.C-P=15.0 Hz), 134.3 (d, J.sub.C-P=10.3 Hz), 133.0 (d, J.sub.C-P=9.4 Hz), 138.6 (d, J.sub.C-P=2.8 Hz).
(142) 4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)phenyldiethylphosphonate; .sup.1H NMR (400 MHz, CDCl.sub.3) 1.30 (t, J=7.2 Hz, 6H), 1.32 (s, 12H), 3.98-4.18 (m, 4H), 7.78 (dd, J=13.0, 8.0 Hz, 2H), 7.88 (dd, J=8.0, 4.0 Hz, 2H); .sup.13C NMR (100 MHz, CDCl.sub.3) 16.3 (d, J.sub.C-P=6.6 Hz), 24.8, 62.0 (d, J.sub.C-P=5.8 Hz), 84.0, 130.9 (d, J.sub.C-P=185 Hz), 130.8 (d, J.sub.C-P=9.4 Hz), 134.5 (d, J.sub.C-P=15.0 Hz).
3,5-Bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2yl)phenyldiethylphosphonate
(143) ##STR00056##
(144) 16% yield; colorless solid; .sup.1H NMR (400 MHz, CDCl.sub.3) 1.31 (t, J=7.2 Hz, 6H), 1.33 (s, 24H), 3.99-4.20 (m, 4H), 8.32 (dd, J=13.0, 1.4 Hz, 1H), 8.40 (d, J=1.4 Hz, 1H); .sup.13C NMR (100 MHz, CDCl.sub.3) 16.3 (d, J.sub.C-P=6.6 Hz), 24.8, 62.0 (d, J.sub.C-P=5.6 Hz), 84.0, 127.0 (d, J.sub.C-P=187 Hz), 140.7 (d, J.sub.C-P=10.3 Hz), 144.9 (d, J.sub.C-P=1.9 Hz); .sup.11B NMR (130 MHz, CDCl.sub.3) 31.0; .sup.31P NMR (153 MHz, CDCl.sub.3) 30.4; IR (KBr, /cm.sup.1) 2977, 1597, 1389, 1331, 1318, 1272, 1248, 1214, 1168, 1141, 1048, 1019, 964, 952, 886, 848, 790, 718, 691, 662; HRMS (ESI.sup.+) Calcd for C.sub.22H.sub.37B.sub.2NaO.sub.7P ([M+Na].sup.+) 489.2361, Found 489.2384.
(145) By using the ligand used in (1), the following compounds ((2) to (9)) were obtained in the same manner as the method of (1).
(2) (2-Methoxy-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyldiethylphosphonate and (2-methoxy-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyldiethylphosphonate
(146) ##STR00057##
(147) 59% yield [meta/para=0.54]; pale brown oil; .sup.11B NMR (130 MHz, CDCl.sub.3) 30.7; .sup.31P NMR (158 MHz, CDCl.sub.2) 28.1, 28.5; IR (neat, /cm.sup.1) 2979, 2935, 2909, 1597, 1550, 1402, 1462, 1393, 1357, 1325, 1244, 1164, 1146, 1108, 1078, 1055, 1029, 965, 903, 851, 777, 760, 692, 675; HRMS (ESI.sup.+) Calcd for C.sub.17H.sub.26BNaO.sub.6P ([M+Na].sup.+) 393.1614, Found 393.1599.
(148) (2-Methoxy-5-(4,4,5,5-tetrarmethyl-1,3,5-dioxaborolan-2-yl)phenyldiethylphosphonate: .sup.1H NMR (500 MHz, CDCl.sub.3) 1.15-1.45 (m, 18H), 3.88 (s, 3H), 4.00-4.25 (m, 4H), 6.85-6.92 (m, 1H), 7.91 (d, J=8.6 Hz, 1H), 8.24 (d, J=14.9 Hz, 1H), .sup.13C NMR (125 MHz, CDCl.sub.3) 16.3, 24.8, 55.6, 62.0 (d, J.sub.C-P=4.8 Hz), 83.7, 110.3 (d, J.sub.C-P=8.4 Hz), 115.8 (d, J.sub.C-P=186 Hz), 141.1, 142.0 (d, J.sub.C-P=7.2 Hz), 163.5 (d, J.sub.C-P=2.4 Hz).
(149) (2Methoxy-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyldiethylphosphonate: .sup.1H NMR (500 MHz, CDCl.sub.3) 1.15-1.45 (m, 18H), 3.91 (s, 3H), 4.00-4.25 (m, 4H), 7.31 (d, J=6.3 Hz, 1H), 7.41 (dd, J=7.5, 3.4 Hz, 1H), 7.78 (dd, J=14.3, 7.5 Hz, 1H); .sup.13C NMR (125 MHz, CDCl.sub.3) 16.2, 24.8, 55.8, 62.1 (d, J.sub.C-P=6.0 Hz), 84.1, 116.5 (d, J.sub.C-P=8.4 Hz), 119.0 (d, J.sub.C-P=185 Hz), 126.5 (d, J.sub.C-P=14.4 Hz), 134.2 (d, J.sub.C-P=7.2 Hz), 160.5 (d, J.sub.C-P=2.4 Hz).
(3) (2-Methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyldiethylphosphonate and (2-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyldiethylphosphonate
(150) ##STR00058##
(151) 66% yield [meta/para=9.0]; pale yellow oil; .sup.11B NMR (130 MHz, CDCl.sub.3) 30.9; .sup.31P HMR (158 MHz, CDCl.sub.3) 30.7, 30.2; IR (neat, /cm.sup.1) 2979, 2931, 2906, 1603, 1480, 1445, 1386, 1360, 1317, 1248, 1165, 1147, 1109, 1049, 1023, 963, 851, 795, 728, 674; HRMS (ESI.sup.+) Calcd for C.sub.17H.sub.28BNaO.sub.5P ([M+Na].sup.+) 377.1665, Found 337.1666.
(152) (2-Methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyldiethylphosphonate: .sup.1H NMR (500 MHz, CDCl.sub.3) 1.23-1.38 (m, 18H), 2.56 (s, 3H), 4.01-4.18 (m, 4H), 7.24 (dd, J=7.5, 5.2 Hz, 1H), 7.81 (d, J=7.5 Hz, 1H), 8.33 (d, J=14.4 Hz, 1H); .sup.13C HMR (100 MHz, CDCl.sub.3) 16.2 (d, J.sub.C-P=6.1 Hz), 21.4 (d, J.sub.C-P=3.3 Hz), 24.8, 61.7 (d, J.sub.C-P=5.6 Hz), 83.8, 126.2 (d, J.sub.C-P=183 Hz), 130.5 (d, J.sub.C-P=14.1 Hz), 138.6 (d, J.sub.C-P=2.8 Hz), 140.4 (d, J.sub.C-P=10.3 Hz), 144.8 (d, J.sub.C-P=10.3 Hz).
(153) (2-Methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2yl)phenyldiethylphosphonate; .sup.1H HMR (500 MHz, CDCl.sub.3) 1.23-1.38 (m, 1.8H), 2.56 (s, 3H), 4.00-4.17 (m, 4H), 7.65-7.70 (m, 2H), 7.88 (dd, J=14.3, 8.0 Hz, 1H); NMR (100 MHz, CDCl.sub.3) 16.2 (d, J.sub.C-P=6.6 Hz), 20.9 (d, J.sub.C-P=2.8 Hz), 24.8, 61.7 (d, J.sub.C-P=5.6 Hz), 84.0, 129.4 (d, J.sub.C-P=181 Hz), 131.5 (d, J.sub.C-P=14.4 Hz), 133.0 (d, J.sub.C-P=10.8 Hz), 137.2 (d, J.sub.C-P=14.4 Hz), 140.7 (d, J.sub.C-P=10.8 Hz).
(4) (2-Bromo-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl) diethylphosphonate
(154) ##STR00059##
(155) 65% yield; pale yellow oil; .sup.1H HMR (400 MHz, CDCl.sub.3) 1.29 (s, 12H), 1.32 (t, J=7.2 Hz, 6H), 4.02-4.22 (m, 4H), 7.63 (dd, J=8.1, 4.9 Hz, 1H), 7.73 (dd, J=8.1, 1.3 Hz, 1H), 8.41 (d, J=13.9, 1.3 Hz, 1H); .sup.13C NMR (125 MHz, CDCl.sub.3) 16.2 (d, J.sub.C-P=7.2 Hz), 24.8, 62.4 (d, J.sub.C-P=4.8 Hz), 84.2, 128.6 (d, J.sub.C-P=4.8 Hz), 128.7 (d, J.sub.C-P=191 Hz), 133.6 (d, J.sub.C-P=9.6 Hz), 139.5 (d, J.sub.C-P=2.4 Hz), 142.6 (d, J.sub.C-P=8.4 Hz); .sup.11B NMR (130 MHz, CDCl.sub.3) 30.9; .sup.31P NMR (158 MHz, CDCl.sub.3) 26.1; IR (neat, /cm.sup.1) 2979, 2932, 2906, 1585, 1552, 1476, 1444, 1373, 1356, 1319, 1262, 1251, 1214, 1166, 1145, 1098, 1054, 1024, 964, 845, 796, 766, 726, 671; HRMS (ESI.sup.+) Calcd for C.sub.16H.sub.25BBrNaO.sub.5P ([M+Na].sup.+) 441.0614, Found 441.0602.
(5) (5-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)-2-trifluoromethylphenyl) diethylphosphonate
(156) ##STR00060##
(157) 30% yield; pale yellow solid; .sup.1H NMR (500 MHz, CDCl.sub.3) 1.28-1.40 (m, 18H), 4.07-4.26 (m, 4H), 7.78 (dd, J=8.0, 5.7 Hz, 1H), 8.05 (d, J=8.0 Hz, 1H), 8.64 (d, J=14.9 Hz, 1H); .sup.13C NMR (100 MHz, CDCl.sub.3) 16.1 (d, J.sub.C-P=6.6 Hz), 24.8, 62.6 (d, 6.1 Hz), 34.5, 121.9 (qd, J.sub.C-P, C-P=273, 4.7 Hz), 126.0 (d, J.sub.C-P=184 Hz), 127.4 (dq, J.sub.C-P, C-P=6.1, 10.8 Hz), 134.3 (qd, J.sub.C-P=32.4, 7.5 Hz), 138.6 (d, J.sub.C-P=2.8 Hz), 142.1 (d, J.sub.C-P=15.4 Hz); .sup.11B NMR (130 MHz, CDCl.sub.3) 30.8; .sup.19F NMR (368 MHz, CDCl.sub.3) 60.9 (s, 3F); .sup.31P NMR (158 MHz, CDCl.sub.3) 26.1; IR (KBr, /cm.sup.1) 2993, 1377, 1362, 1325, 1308, 1280, 1244, 1148, 1135, 1104, 1059, 1029, 977, 964, 951, 849, 768, 682; HRMS (ESI.sup.+) Calcd for C.sub.17H.sub.25BF.sub.3NaO.sub.5P ([M+Na].sup.+) 431.1382, Found 431.1379.
(158) (6) N,N,N,N-Tetraethyl-P-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)phosphonic diamide
(159) ##STR00061##
(160) 29% yield; pale brown oil; .sup.1H NMR (500 MHz, CDCl.sub.3) 1.04 (t, J=7.5 Hz, 12H), 1.33 (s, 12H), 3.00-3.13 (m, 8H), 7.35-7.47 (m, 1H), 7.84 (dd, J=11.5, 7.5 Hz, 1H), 7.88 (d, J=6.9 Hz, 1H), 8.19 (d, J=11.5 Hz, 1H); .sup.13C NMR (125 MHz, CDCl.sub.3) 13.6 (d, J.sub.C-P=2.4 Hz), 24.9, 38.4 (d, J.sub.C-P=4.8 Hz), 83.9, 127.5 (d, J.sub.C-P=12.0 Hz), 132.4 (d, J.sub.C-P=158 Hz), 134.5, (d, J.sub.C-P=8.4 Hz), 137.2, 138.3 (d, J.sub.C-P=8.4 Hz); .sup.11B NMR (130 MHz, CDCl.sub.3) 31.5; .sup.31P NMR (158 MHz, CDCl.sub.3) 39.4; IR (neat, /cm.sup.1) 2973, 2932, 2871, 1594, 1470, 1383, 1357, 1317, 1262, 1216, 1187, 1015, 945, 866, 841, 791, 739, 711, 671, 656; HRMS (ESI.sup.+) Calcd for C.sub.20H.sub.37BN.sub.2O.sub.3P ([M+H].sup.+) 395.2635, Found 395.2639.
N,N,N,N-Tetraethyl-P-(3,5-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)phosphonic diamide
(161) ##STR00062##
(162) 9% yield; pale yellow solid; .sup.1H NMR (500 MHz, CDCl.sub.3) 1.03 (t, J=6.9 Hz, 12H), 1.31 (s, 24H), 2.98-3.16 (m, 8H), 8.27 (d, J=12.1 Hz, 2H); 8.32 (s, 1H); .sup.13C NMR (125 MHz, CDCl) 13.6 (d, J.sub.C-P=2.4 Hz), 24.8, 38.3 (d, J.sub.C-P=3.6 Hz), 83.8, 131.8 (d, J.sub.C-P=154 Hz), 141.1 (d, J.sub.C-P=9.6 Hz), 143.5 (d, J.sub.C-P=2.4 Hz); .sup.11B NMR (130 MHz, CDCl.sub.3) 31.3; .sup.31P NMR (158 MHz, CDCl.sub.3) 39.5 IR (KBr, /cm.sup.1) 2978, 2932, 2873, 1594, 1458, 1383, 1327, 1313, 1272, 1220, 1189, 1163, 1144, 1020, 967, 945, 887, 847, 720, 659; HRMS (ESI.sup.+) Calcd for C.sub.26H.sub.47B.sub.2N.sub.2NaO.sub.5P ([M+Na].sup.+) 543.3306, Found 543.3312.
(7) Dicyclohexyl(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2yl)phenyl)phosphine oxide
(163) ##STR00063##
(164) 39% yield; pale brown solid; .sup.1H NMR (500 MHz, CDCl.sub.3) 1.05-1.37 (m, 21H), 1.50-1.88 (m, 8H), 1.90-2.20 (m, 4H), 2.25-2.46 (m, 1H), 7.40-7.51 (m, 1H), 7.68-7.83 (m, 1H), 7.93 (d, J=6.9 Hz, 1H), 7.98-8.07 (m, 1H); .sup.13C NMR (125 MHz, CDCl.sub.3) 24.6, 24.9, 25.5, 25.8, 26.3-26.5 (m, 2C), 35.2 (d, J.sub.C-P=66.0 Hz), 84.0, 127.4-127.6 (m), 129.1 (d, J.sub.C-P=85.2 Hz), 134.1-134.4 (m), 137.2-137.5 (m), 137.6; .sup.11B NMR (130 MHz, CDCl.sub.3) 30.9; .sup.31P NMR (158 MHz, CDCl.sub.3) 56.7 IR (KBr, /cm.sup.1) 2979, 29.30, 2853, 1594, 1449, 1404, 1359, 1316, 1278, 1211, 1166, 1145, 1130, 1115, 1077, 963, 891, 853, 840, 759, 731, 709, 671; HRMS (ESI.sup.+) Calcd for C.sub.24H.sub.38BNaO.sub.3P ([M+Na].sup.+) 439.2549, Found 439.2567.
Dicyclohexyl(3,5-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)phosphine oxide
(165) ##STR00064##
(166) 35% yield; pale brown solid; .sup.1NMR (500 MHz, CDCl.sub.3) 1.08-1.36 (m, 33H), 1.51-1.86 (m, 8H), 1.94-2.13 (m, 4H), 2.23-2.45 (m, 1H), 8.11 (d, J=9.8 Hz, 1H), 8.37 (s, 1H); .sup.13C NMR (125 MHz, CDCl.sub.3) 24.7, 24.8, 25.5, 25.8, 26.2-26.5 (m, 2C), 35.3 (d, J.sub.C-P=67.2 Hz), 84.0, 128.5 (d, J.sub.C-P=85.2 Hz), 140.2 (d, J.sub.C-P=7.2 Hz), 144.0; .sup.11B NMR (130 MHz, CDCl.sub.3) 31.2; .sup.31P NMR (158 MHz, CDCl.sub.3) 56.4; IR (KBr, /cm.sup.1) 2977, 2929, 2853, 1594, 1449, 1383, 1329, 1272, 1215, 1176, 1143, 966, 388, 849, 716; HRMS (ESI.sup.+) Calcd for C.sub.30H.sub.50B.sub.2O.sub.5P ([M+H].sup.+) 543.3582, Found, 543.3588.
(8) Dicyclohexyl(2-methoxy-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)phosphine oxide
(167) ##STR00065##
(168) 99% yield; pale yellow solid; NMR (400 MHz, CDCl.sub.3) 1.14-1.19 (m, 4H), 1.21-1.42 (m, 16H), 1.44-1.51 (m, 4B), 1.64-1.68 (m, 4H), 1.80-1.84 (m, 2H), 2.03-2.17 (m, 4H), 3.86 (s, 3H), 6.87 (dd, J=8.7, 4.7 Hz, 1H), 7.91 (d, J=8.7 Hz, 1H), 8.36 (d, J=11.7 Hz, 1H); .sup.13C NMR (100 MHz, CDCl.sub.3) 24.9, 25.7 (d, 3.8 Hz), 25.9, 26.1 (d, J.sub.C-P=3.8 Hz), 26.6 (d, J.sub.C-P=12.3 Hz), 26.9 (d, J.sub.C-P=14.1 Hz), 36.9 (d, J.sub.C-P=67.7 Hz), 55.1, 83.7, 109.3 (d, J.sub.C-P=6.9 Hz), 118.3 (d, J.sub.C-P=83.8 Hz), 140.1 (d, J.sub.C-P=1.9 Hz), 142.8 (d, J.sub.C-P=3.8 Hz), 161.5 (d, J.sub.C-P=5.6 Hz); .sup.11B NMR (130 MHz, CDCl.sub.3) 29.8; .sup.31P NMR (158 MHz, CDCl.sub.3) 59.5; IR (KBr, /cm.sup.1) 2978, 2931, 2852, 1594, 1448, 1407, 1385, 1357, 1317, 1279, 1266, 1250, 1212, 1147, 1104, 1077, 1014, 964, 887, 851, 824, 750, 673; HRMS (ESI.sup.+) Calcd for C.sub.25H.sub.40BNaO.sub.4P ([M+Na].sup.+) 469.2655, Found 469.2668.
(9) Dicyclohexyl(2-chloro-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)phosphine oxide
(169) ##STR00066##
(170) 99% yield; pale yellow solid; .sup.1H NMR (400 MHz, CDCl.sub.3) 1.16-1.21 (m, 4H) 1.24-1.36 (m, 18H), 1.59-1.70 (m, 6H), 1.83-1.86 (m, 2H), 2.07-2.10 (m, 2H), 2.27-2.36 (m, 2H), 7.36 (dd, J=7.9, 3.6 Hz, 1H), 7.81 (d, J=7.9 Hz, 1H), 8.49 (d, J=10.5 Hz, 1H); .sup.13C NMR (100 MHz, CDCl.sub.3) 24.9, 25.7 (d, J.sub.C-P=1.4 Hz), 26.2 (d, J.sub.C-P=3.3 Hz), 26.3 (d, J.sub.C-P=3.8 Hz), 26.5 (d, J.sub.C-P=12.7 Hz), 26.7 (d, J.sub.C-P=13.6 Hz), 37.4 (d, J.sub.C-P=13.6 Hz), 84.2, 129.3 (d, J.sub.C-P=6.1 Hz), 130.1, 137.3 (d, J.sub.C-P=6.1 Hz), 138.8 (d, J.sub.C-P=2.3 Hz), 143.1 (d, J.sub.C-P=4.7 Hz); .sup.11B NMR (130 MHz, CDCl.sub.3) 30.5; .sup.31P NMR (158 MHz, CDCl.sub.3) 59.4; IR (KBr, /cm.sup.1) 2978, 29323, 2852, 1583, 1557, 1448, 1371, 1356, 1317, 1259, 1214, 1183, 1169, 1143, 1113, 1097, 1031, 964, 845, 755, 726, 671; HRMS (ESI.sup.+) Calcd for C.sub.24H.sub.38BClO.sub.3P ([M+H].sup.+) 451.2340, Found 451.2341.