PREPARATION METHOD FOR 1,3-DISUBSTITUTED ALLENE COMPOUND AT ROOM TEMPERATURE BASED ON METAL CARBENE CATALYTIC SYSTEM

Abstract

Disclosed are a preparation method for a 1,3-disubstituted allene compound at room temperature based on a metal carbene catalyst, comprising: reacting terminal alkynes, aldehydes and amines in an organic solvent under the action of a gold catalyst and a molecular sieve, and then synthesizing a 1,3-disubstituted allene compound at room temperature. The method of the present invention is simple to operate, raw materials and reagents are easily obtained, reaction conditions are mild, substrate universality is wide, functional group compatibility is good, yield is high (36-93%), the method is scalable (11 g), and practicability is strong. The 1,3-disubstituted allene compound obtained in the present invention may be used as an important intermediate to construct -caprolactone, trans-allyl alcohol, other allene-derived compounds and natural product molecules and the like.

Claims

1. A method for preparing 1,3-disubstituted allene compound based on a gold carbene catalytic system at room temperature, wherein, terminal alkynes (2) with different substituents, aldehydes (1) and amines (3) in an organic solvent under the action of a gold carbene catalyst and a molecular sieve to generate 1,3-disubstituted allene compound at room temperature, the reaction process is shown in the following reaction formula (a): ##STR00085## wherein, R.sup.1 is C1-C10 alkyl group, C1-C10 alkyl group with functional groups, phenyl, aryl and heterocyclic groups; R.sup.2 is C1-C10 alkyl group, C1-C10 alkyl group with functional groups, phenyl, aryl and heterocyclic groups; the functional groups in R.sup.1 and R.sup.2 are selected from carbon-carbon double bond, halogen atom, hydroxyl, silyl ether, carbonyl, nitrile, ester and amido groups; the said aryl groups are phenyl and polyphenyl cyclosubstituented groups with electron-donating or electron-withdrawing substituents in the ortho, meta and para positions; the said electron-donating substituents comprises alkyl, methoxy, benzyloxy and boronate groups, and the said electron-withdrawing substituents comprises halogen, nitrile, ester, trifluoromethyl and nitro groups; the said heterocyclic groups are furyl, benzofuryl, thienyl, pyridyl, indolyl and indazolyl.

2. The method of claim 1, wherein, the method specifically comprises the following steps: under an argon atmosphere, molecular sieves, gold carbene catalysts and a certain volume of organic solvent are added in sequence to the dry reaction tube; the aldehydes (1), amines (3) and terminal alkynes (2) are then added in sequence with stirring, reaction is carried out for 24-72 hours at room temperature; after the reaction is complete, the reaction mixture was filtered through a short silica gel column and washed with a certain volume of diethyl ether; after the mixture was concentrated, it was subjected to flash column chromatography to obtain 1,3-disubstituted allene compound; wherein, the organic solvent of a certain volume refers to the amount of the terminal alkynes (2) shown in the formula (a) as a benchmark, the amount of the organic solvent is 0.5-5 mL/mmol; wherein, the room temperature means 10-40 C.; the said certain volume of diethyl ether refers to the amount of terminal alkynes (2) shown in the formula (a) as a benchmark, the amount of the said diethyl ether is 10-100 mL/mol.

3. The method of claim 1, wherein, the amines (3) is selected from morpholine(3a), piperidine(3b), pyrrolidine(3c), 1,2,3,4-tetrahydroquinoline(3d), 1,2,3,4-tetrahydroisoquinoline(3e), 1-methyl-1,2,3,4-tetrahydroisoquinoline(3f), diethylamine(3g), diallylamine(3h), dicyclohexylamine(3i) and diisopropylamine(3j).

4. The method of claim 1, wherein, the gold carbene catalyst is selected from one or more of the following structures Au1-Au3, wherein, R is C1-C30 alkyl group, C1-C30 alkyl group with functional groups, phenyl, aryl, and heterocyclic; the functional group is selected from carbon-carbon double bond, carbon-carbon triple bond, halogen atom, hydroxyl, carboxyl, amino, silyl ether, carbonyl, nitrile, ester and amido groups; the said aryl refers to phenyl and polyphenyl cyclosubstituents with electron-donating or electron-withdrawing substituents in the ortho, meta, and para positions; the electron-donating substituents include alkyl, alkoxy and boronate groups, and the electron-withdrawing substituents include halogen, nitrile, ester, trifluoromethyl and nitro groups; among them, X is a counter anion, including halogen anion, hydroxide anion, bis(trifluoromethanesulfonyl)imide anion, methanesulfonate anion, trifluoromethanesulfonate anion, p-methylbenzenesulfonate anion, perchlorate anion, tetrafluoroborate anion, hexafluorophosphate anion and hexafluoroantimonate anion; ##STR00086##

5. The method of claim 1, wherein, the molecular sieve is from 3 molecular sieve, 4 molecular sieve and 5 molecular sieve.

6. The method of claim 1, wherein, the organic solvent is selected from one or more of 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoropropanol, 2,2,3,3,3-pentafluoropropanol and 1,1,1,3,3,3-hexafluoroisopropanol.

7. The method of claim 1, wherein, the mol ratio of the terminal alkynes (2), aldehydes (1), amines (3) and gold carbene catalyst is 1.0:(1.0-1.8):(1.0-1.4):(0.01-0.1); and/or, the amount of the molecular sieve is 100-500 mg/mmol, based on the amount of the terminal alkynes (2); and/or, the amount of the organic solvent is 0.5-5 mL/mmol, based on the amount of the terminal alkynes (2).

8. The method of claim 1, wherein, the room temperature refers to 10-60 C.; the reaction time is 24-72 hours.

9. A class of 1,3-disubstituted allene compound, wherein, its structure is shown in the following formula 4: ##STR00087## wherein, R.sup.1 is C1-C10 alkyl group, C1-C10 alkyl group with functional groups, phenyl, aryl and heterocyclic groups; R.sup.2 is C1-C10 alkyl group, C1-C10 alkyl group with functional groups, phenyl, aryl and heterocyclic groups; the functional groups in R.sup.1 and R.sup.2 are selected from carbon-carbon double bond, halogen atom, hydroxyl, silyl ether, carbonyl, nitrile, ester and amido groups; the aryl groups are phenyl and polyphenyl cyclosubstituented groups with electron-donating or electron-withdrawing substituents in the ortho, meta and para positions; the said electron-donating substituents comprises alkyl, methoxy, benzyloxy and boronate groups, and the said electron-withdrawing substituents comprises halogen, nitrile, ester, trifluoromethyl and nitro groups; the said heterocyclic groups are furyl, benzofuryl, thienyl, pyridyl, indolyl and indazolyl.

10. The application of the 1,3-disubstituted allene compound according to claim 9 in the preparation of -caprolactone, trans-allyl alcohol, other allene derived compounds, and natural product molecules.

11. The method of claim 2, wherein, the amines (3) is selected from morpholine(3a), piperidine(3b), pyrrolidine(3c), 1,2,3,4-tetrahydroquinoline(3d), 1,2,3,4-tetrahydroisoquinoline(3e), 1-methyl-1,2,3,4-tetrahydroisoquinoline(3f), diethylamine(3g), diallylamine(3h), dicyclohexylamine(3i) and diisopropylamine(3j).

12. The method of claim 2, wherein, the gold carbene catalyst is selected from one or more of the following structures Au1-Au3, wherein, R is C1-C30 alkyl group, C1-C30 alkyl group with functional groups, phenyl, aryl, and heterocyclic; the functional group is selected from carbon-carbon double bond, carbon-carbon triple bond, halogen atom, hydroxyl, carboxyl, amino, silyl ether, carbonyl, nitrile, ester and amido groups; the said aryl refers to phenyl and polyphenyl cyclosubstituents with electron-donating or electron-withdrawing substituents in the ortho, meta, and para positions; the electron-donating substituents include alkyl, alkoxy and boronate groups, and the electron-withdrawing substituents include halogen, nitrile, ester, trifluoromethyl and nitro groups; among them, X is a counter anion, including halogen anion, hydroxide anion, bis(trifluoromethanesulfonyl)imide anion, methanesulfonate anion, trifluoromethanesulfonate anion, p-methylbenzenesulfonate anion, perchlorate anion, tetrafluoroborate anion, hexafluorophosphate anion and hexafluoroantimonate anion; ##STR00088##

13. The method of claim 2, wherein, the molecular sieve is from 3 molecular sieve, 4 molecular sieve and 5 molecular sieve.

14. The method of claim 2, wherein, the organic solvent is selected from one or more of 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoropropanol, 2,2,3,3,3-pentafluoropropanol and 1,1,1,3,3,3-hexafluoroisopropanol.

Description

PREFERRED EMBODIMENTS OF THE INVENTION

[0056] The following examples are given to further illustrating the specific solutions of the present invention. The process, conditions, experimental methods, and so on for implementing the present invention are all general knowledge and common knowledge in the field except for the contents specifically mentioned below, and the present invention has no special limitation.

Example 1

##STR00038##

[0057] Wherein mol represents mole, equiv. represents equivalent, 5 MS represents 5 molecular sieve, TFE represents 2,2,2-trifluoroethanol, Ar represents argon atmosphere, yield represents yield.

[0058] Under the protection of argon atmosphere, 5 molecular sieves (250.4 mg), Au3d (43.5 mg, 0.05 mmol) and 2,2,2-trifluoroethanol (1 mL) were added in sequence to a dry reaction tube. Then, under stirring, aldehyde 1a (191.3 mg, 1.8 mmol), 1-methyl-1,2,3,4-tetrahydroisoquinoline 3f (176.6 mg, 1.2 mmol) and terminal alkyne 2a (110.0 mg, 1.0 mmol) were added in sequence. After reacting at room temperature for 24 hours, the reaction solution was filtered through a short silica gel column and the filter cake was washed with diethyl ether (30 mL), concentrated, purified by flash column chromatography (eluent:petroleum ether) to afford an allene product 4aa (168.7 mg, 84% yield): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): =7.36-7.26 (m, 4H, ArH), 7.22-7.14 (m, 1H, ArH), 6.12 (dt, J.sub.1=6.1 Hz, J.sub.2=3.0 Hz, 1H, CH), 5.56 (q, J=6.7 Hz, 1H, CH), 2.12 (qd, J.sub.1=7.1 Hz, J.sub.2=2.9 Hz, 2H, CH.sub.2), 1.53-1.41 (m, 2H, CH.sub.2), 1.41-1.18 (m, 6H, CH.sub.23), 0.88 (t, J=6.8 Hz, 3H, CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): =205.1, 135.1, 128.5, 126.55, 126.52, 95.1, 94.5, 31.6, 29.1, 28.9, 28.7, 22.7, 14.1; IR (neat): =2956, 2924, 2854, 1949, 1598, 1495, 1458 cm.sup.1; MS (FI) m/z (%): 200 (M.sup.+); HRMS Calcd. for C.sub.15H.sub.20 (M.sup.+): 200.1560, found 200.1564.

Example 2

##STR00039##

[0059] The operation is the same as Example 1. 5 molecular sieves (250.1 mg), Au3d (43.4 mg, 0.05 mmol), aldehyde 1a (191.4 mg, 1.8 mmol), 1-methyl-1,2,3,4-tetrahydroisoquinoline 3f (176.5 mg, 1.2 mmol) and terminal alkyne 2b (166.1 mg, 1.0 mmol) were reacted in 2,2,2-trifluoroethanol (1 mL) to afford an allene product 4ab (205.5 mg, 80% yield) (purified by flash column chromatography (eluent:petroleum ether)): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): =7.33-7.25 (m, 4H, ArH), 7.21-7.12 (m, 1H, ArH), 6.11 (dt, J.sub.1=6.1 Hz, J.sub.2=3.1 Hz, 1H, CH), 5.56 (q, J=6.5 Hz, 1H, CH), 2.12 (qd, J.sub.1=7.0 Hz, J.sub.2=2.7 Hz, 2H, CH.sub.2), 1.52-1.41 (m, 2H, CH.sub.2), 1.40-1.12 (m, 14H, CH.sub.27), 0.88 (t, J=6.8 Hz, 3H, CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): =205.1, 135.2, 128.5, 126.56, 126.55, 95.1, 94.5, 31.9, 29.64, 29.60, 29.4, 29.3, 29.20, 29.17, 28.8, 22.7, 14.1; IR (neat): =2922, 2852, 1949, 1598, 1495, 1460, 1071 cm.sup.1; MS (70 eV, EI) m/z (%): 256 (M.sup.+, 1.02), 130 (100).

Example 3

##STR00040##

[0060] The operation is the same as Example 1. 5 molecular sieves (251.0 mg), Au3d (43.6 mg, 0.05 mmol), aldehyde 1a (191.2 mg, 1.8 mmol), 1-methyl-1,2,3,4-tetrahydroisoquinoline 3f (176.8 mg, 1.2 mmol) and terminal alkyne 2c (67.5 mg, 1.0 mmol) were reacted in 2,2,2-trifluoroethanol (1 mL) to afford an allene product 4ac (124.8 mg, 80% yield) (purified by flash column chromatography (eluent:petroleum ether)): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): =7.33-7.23 (m, 4H, ArH), 7.21-7.13 (m, 1H, ArH), 6.20 (d, J=6.0 Hz, 1H, CH), 5.43 (t, J=6.8 Hz, 1H, CH), 1.39-1.25 (m, 1H, CH), 0.80-0.68 (m, 2H, CH.sub.2), 0.51-0.37 (m, 2H, CH.sub.2); .sup.13C NMR (100 MHz, CDCl.sub.3): =204.8, 134.9, 128.5, 126.8, 126.6, 99.4, 96.2, 9.4, 7.0, 6.8; IR (neat): =3081, 3004, 1946, 1597, 1492, 1458, 1423, 1251, 1047, 1020 cm.sup.1; MS (70 eV, EI) m/z (%): 156 (M.sup.+, 86.83), 115 (100).

Example 4

##STR00041##

[0061] The operation is the same as Example 1. 5 molecular sieves (250.9 mg), Au3d (43.4 mg, 0.05 mmol), aldehyde 1a (191.2 mg, 1.8 mmol), 1-methyl-1,2,3,4-tetrahydroisoquinoline 3f (176.5 mg, 1.2 mmol) and terminal alkyne 2d (118.8 mg, 1.0 mmol) were reacted in 2,2,2-trifluoroethanol (1 mL) to afford an allene product 4ad (111.0 mg, 54% yield) (purified by flash column chromatography (eluent:petroleum ether)): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): =7.35-7.24 (m, 8H, ArH), 7.24-7.15 (m, 2H, ArH), 6.17 (dt, J.sub.1=5.5 Hz, J.sub.2=2.8 Hz, 1H, CH), 5.72 (q, J=7.1 Hz, 1H, CH), 3.47 (dd, J.sub.1=7.4 Hz, J.sub.2=2.2 Hz, 2H, CH.sub.2); .sup.13C NMR (100 MHz, CDCl.sub.3): =205.7, 140.0, 134.6, 128.5, 128.4, 126.8, 126.7, 126.3, 94.9, 94.4, 35.5; IR (neat): =3028, 1948, 1599, 1493, 1454, 1072, 1028 cm.sup.1; MS (70 eV, EI) m/z (%): 206 (M.sup.+, 100).

Example 5

##STR00042##

[0062] The operation is the same as Example 1. 5 molecular sieves (250.1 mg), Au3d (43.3 mg, 0.05 mmol), aldehyde 1a (191.2 mg, 1.8 mmol), 1-methyl-1,2,3,4-tetrahydroisoquinoline 3f (176.6 mg, 1.2 mmol) and the terminal alkyne 2e (102.3 mg, 1.0 mmol) were reacted in 2,2,2-trifluoroethanol (1 mL) to afford an allene product 4ae (118.8 mg, 62% yield) (purified by flash column chromatography (eluent:petroleum ether)): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): =7.43-7.26 (m, 8H, ArH), 7.26-7.16 (m, 2H, ArH), 6.59 (s, 2H, CH2); .sup.13C NMR (100 MHz, CDCl.sub.3): =207.7, 133.5, 128.7, 127.3, 127.0, 98.4; IR (neat): =3027, 1935, 1596, 1491, 1449, 1254, 1071, 1027 cm.sup.1; MS (70 eV, EI) m/z (%): 192 (M.sup.+, 100).

Example 6

##STR00043##

[0063] The operation is the same as Example 1. 5 molecular sieves (250.6 mg), Au3d (43.2 mg, 0.05 mmol), aldehyde 1b (223.1 mg, 1.8 mmol), 1-methyl-1,2,3,4-tetrahydroisoquinoline 3f (176.9 mg, 1.2 mmol) and terminal alkyne 2a (110.0 mg, 1.0 mmol) were reacted in 2,2,2-trifluoroethanol (1 mL) to afford an allene product 4ba (185.6 mg, 85% yield) (purified by flash column chromatography (eluent:petroleum ether)): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): =7.29-7.17 (m, 2H, ArH), 7.03-6.91 (m, 2H, ArH), 6.08 (dt, J.sub.1=6.1 Hz, J.sub.2=3.1 Hz, 1H, CH), 5.56 (q, J=6.7 Hz, 1H, CH), 2.17 (qd, J.sub.1=7.1 Hz, J.sub.2=3.0 Hz, 2H, CH.sub.2), 1.53-1.41 (m, 2H, CH.sub.2), 1.41-1.18 (m, 6H, CH.sub.23), 0.88 (t, J=6.6 Hz, 3H, CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): =204.9 (d, J=2.5 Hz), 161.7 (d, J=244.5 Hz), 131.1 (d, J=3.2 Hz), 127.9 (d, J=8.1 Hz), 115.4 (d, J=21.4 Hz), 95.3, 93.6, 31.6, 29.1, 28.9, 28.8, 22.7, 14.0; .sup.19F NMR (376 MHz, CDCl.sub.3): =116.5; IR (neat): =2925, 2855, 1948, 1602, 1506, 1463, 1226, 1154 cm.sup.1; MS (70 eV, EI) m/z (%): 218 (M.sup.+, 2.01), 148 (100).

Example 7

##STR00044##

[0064] The operation is the same as Example 1. 5 molecular sieves (250.6 mg), Au3d (43.4 mg, 0.05 mmol), aldehyde 1c (253.3 mg, 1.8 mmol), 1-methyl-1,2,3,4-tetrahydroisoquinoline 3f (176.5 mg, 1.2 mmol) and terminal alkyne 2a (109.6 mg, 1.0 mmol) were reacted in 2,2,2-trifluoroethanol (1 mL) to afford an allene product 4ca (190.2 mg, 81% yield) (purified by flash column chromatography (eluent:petroleum ether)): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): =7.25 (d, J=8.8 Hz, 2H, ArH), 7.20 (d, J=8.4 Hz, 2H, ArH), 6.07 (dt, J.sub.1=6.4 Hz, J.sub.2=3.1 Hz, 1H, CH), 5.57 (q, J=6.7 Hz, 1H, CH), 2.12 (qd, J.sub.1=7.1 Hz, J.sub.2=3.0 Hz, 2H, CH.sub.2), 1.53-1.41 (m, 2H, CH.sub.2), 1.41-1.18 (m, 6H, CH.sub.23), 0.88 (t, J=6.8 Hz, 3H, CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): =205.2, 133.7, 132.1, 128.6, 127.7, 95.4, 93.7, 31.6, 29.0, 28.8, 28.6, 22.6, 14.0; IR (neat): =2924, 2854, 1949, 1490, 1462, 1090, 1012 cm.sup.1; MS (70 eV, EI) m/z (%): 234 (M.sup.+(.sup.35Cl), 1.40), 236 (M.sup.+(.sup.37Cl), 0.62), 129 (100).

Example 8

##STR00045##

[0065] The operation is the same as Example 1. 5 molecular sieves (250.2 mg), Au3d (43.3 mg, 0.05 mmol), aldehyde 1d (333.1 mg, 1.8 mmol), 1-methyl-1,2,3,4-tetrahydroisoquinoline 3f (176.8 mg, 1.2 mmol) and terminal alkyne 2a (110.0 mg, 1.0 mmol) were reacted in 2,2,2-trifluoroethanol (1 mL) to afford an allene product 4da (215.8 mg, 77% yield) (purified by flash column chromatography (eluent:petroleum ether)): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): =7.40 (d, J=8.4 Hz, 2H, ArH), 7.14 (d, J=8.0 Hz, 2H, ArH), 6.11-6.01 (m, 1H, CH), 5.56 (q, J=6.7 Hz, 1H, CH), 2.12 (qd, J.sub.1=7.1 Hz, J.sub.1=2.4 Hz, 2H, CH.sub.2), 1.52-1.41 (m, 2H, CH.sub.2), 1.41-1.18 (m, 6H, CH.sub.23), 0.88 (t, J=6.8 Hz, 3H, CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): =205.2, 134.2, 131.5, 128.0, 120.1, 95.5, 93.8, 31.6, 29.0, 28.8, 28.6, 22.6, 14.0; IR (neat): =2924, 2853, 1948, 1486, 1463, 1382, 1069, 1009 cm.sup.1; MS (70 eV, EI) m/z (%): 278 (M.sup.+(.sup.79Br), 1.71), 280 (M.sup.+(.sup.81Br), 1.61), 129 (100).

Example 9

##STR00046##

[0066] The operation is the same as Example 1. 5 molecular sieves (250.4 mg), Au3d (43.5 mg, 0.05 mmol), aldehyde 1e (417.2 mg, 1.8 mmol), 1-methyl-1,2,3,4-tetrahydroisoquinoline 3f (176.5 mg, 1.2 mmol) and terminal alkyne 2a (110.1 mg, 1.0 mmol) were reacted in 2,2,2-trifluoroethanol (1 mL) to afford an allene product 4ea (228.3 mg, 70% yield) (purified by flash column chromatography (eluent:petroleum ether)): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): =7.60 (d, J=8.8 Hz, 2H, ArH), 7.02 (d, J=8.0 Hz, 2H, ArH), 6.04 (dt, J.sub.1=6.1 Hz, J.sub.2=3.0 Hz, 1H, CH), 5.56 (q, J=6.8 Hz, 1H, CH), 2.12 (qd, J.sub.1=7.1 Hz, J.sub.2=2.8 Hz, 2H, CH.sub.2), 1.52-1.40 (m, 2H, CH.sub.2), 1.40-1.18 (m, 6H, CH.sub.23), 0.88 (t, J=6.6 Hz, 3H, CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): =205.3, 137.5, 134.8, 128.3, 95.5, 93.9, 91.4, 31.6, 29.0, 28.8, 28.6, 22.6, 14.1; IR (neat): =2923, 2852, 1948, 1483, 1462, 1381, 1058, 1004 cm.sup.1; MS (70 eV, EI) m/z (%): 326 (M.sup.+, 2.26), 129 (100); HRMS Calcd. for C.sub.15H.sub.19I (M.sup.+): 326.0526, found 326.0529.

Example 10

##STR00047##

[0067] The operation is the same as Example 1. 5 molecular sieves (250.4 mg), Au3d (43.3 mg, 0.05 mmol), aldehyde 1f (245.7 mg, 1.8 mmol), 1-methyl-1,2,3,4-tetrahydroisoquinoline 3f (176.6 mg, 1.2 mmol) and terminal alkyne 2a (110.4 mg, 1.0 mmol) were reacted in 2,2,2-trifluoroethanol (1 mL) to afford an allene product 4fa (180.1 mg, 78% yield) (purified by flash column chromatography (eluent:petroleum ether)): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): =7.21 (d, J=8.4 Hz, 2H, ArH), 6.84 (d, J=8.4 Hz, 2H, ArH), 6.08 (dt, J.sub.1=6.1 Hz, J.sub.2=3.0 Hz, 1H, CH), 5.53 (q, J=6.7 Hz, 1H, CH), 3.80 (s, 3H, OCH.sub.3), 2.11 (qd, J.sub.1=7.1 Hz, J.sub.2=3.1 Hz, 2H, CH.sub.2), 1.52-1.41 (m, 2H, CH.sub.2), 1.41-1.18 (m, 6H, CH.sub.23), 0.88 (t, J=6.8 Hz, 3H, CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): =204.4, 158.5, 127.5, 127.4, 114.0, 95.0, 93.9, 55.2, 31.6, 29.1, 28.9, 28.8, 22.6, 14.0; IR (neat): =2925, 2854, 1947, 1607, 1510, 1462, 1300, 1243, 1170, 1035 cm.sup.1; MS (70 eV, EI) m/z (%): 230 (M.sup.+, 20.68), 160 (100).

Example 11

##STR00048##

[0068] The operation is the same as Example 1. 5 molecular sieves (250.3 mg), Au3d (43.3 mg, 0.05 mmol), aldehyde 1g (237.0 mg, 1.8 mmol), 1-methyl-1,2,3,4-tetrahydroisoquinoline 3f (176.3 mg, 1.2 mmol) and terminal alkyne 2a (112.6 mg, 1.0 mmol) were reacted in 2,2,2-trifluoroethanol (1 mL) to afford an allene product 4ga (175.2 mg, 78% yield) (purified by flash column chromatography (eluent:petroleum ether)): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): =7.59-7.53 (m, 2H, ArH), 7.38-7.33 (m, 2H, ArH), 6.13 (dt, J.sub.1=6.3 Hz, J.sub.2=3.1 Hz, 1H, CH), 5.66 (q, J=6.7 Hz, 1H, CH), 2.15 (qd, J.sub.1=7.1 Hz, J.sub.2=3.0 Hz, 2H, CH.sub.2), 1.53-1.41 (m, 2H, CH.sub.2), 1.41-1.20 (m, 6H, CH.sub.23), 0.88 (t, J=6.8 Hz, 3H, CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): =206.5, 140.4, 132.2, 126.9, 119.1, 109.6, 96.0, 93.9, 31.5, 28.9, 28.8, 28.3, 22.5, 14.0; IR (neat): =2925, 2854, 2225, 1946, 1604, 1503, 1462, 1394, 1173 cm.sup.1; MS (70 eV, EI) m/z (%): 225 (M.sup.+, 3.53), 129 (100); HRMS Calcd. for C.sub.16H.sub.19N (M.sup.+): 225.1512, found 225.1515.

Example 12

##STR00049##

[0069] The operation is the same as Example 1. 5 molecular sieves (250.8 mg), Au3d (43.3 mg, 0.05 mmol), aldehyde 1h (301.8 mg, 1.8 mmol), 1-methyl-1,2,3,4-tetrahydroisoquinoline 3f (176.8 mg, 1.2 mmol) and terminal alkyne 2a (112.3 mg, 1.0 mmol) were reacted in 2,2,2-trifluoroethanol (1 mL) to afford an allene product 4ha (199.1 mg, 77% yield) (purified by flash column chromatography (eluent:petroleum ether/ethyl acetate=100/1)): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): =7.96 (d, J 8.0 Hz, 2H, ArH), 7.33 (d, J 8.0 Hz, 2H, ArH), 6.18-6.11 (m, 1H, CH), 5.61 (q, J=6.7 Hz, 1H, CH), 3.90 (s, 3H, OCH.sub.3), 2.14 (qd, J.sub.1=7.1 Hz, J.sub.2=2.7 Hz, 2H, CH.sub.2), 1.53-1.41 (m, 2H, CH.sub.2), 1.41-1.20 (m, 6H, CH.sub.23), 0.88 (t, J=6.6 Hz, 3H, CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): =206.3, 166.9, 140.3, 129.8, 128.1, 126.3, 95.5, 94.2, 51.9, 31.6, 29.0, 28.8, 28.5, 22.6, 14.0; IR (neat): =2925, 2854, 1947, 1718, 1606, 1434, 1272, 1173, 1105 cm.sup.1; MS (70 eV, EI) m/z (%): 258 (M.sup.+, 1.27), 129 (100); HRMS Calcd. for C.sub.17H.sub.22O.sub.2(M.sup.+): 258.1614, found 258.1613.

Example 13

##STR00050##

[0070] The operation is the same as Example 1. 5 molecular sieves (250.5 mg), Au3d (43.4 mg, 0.05 mmol), aldehyde 1i (313.2 mg, 1.8 mmol), 1-methyl-1,2,3,4-tetrahydroisoquinoline 3f (176.8 mg, 1.2 mmol) and terminal alkyne 2a (110.5 mg, 1.0 mmol) were reacted in 2,2,2-trifluoroethanol (1 mL) to afford an allene product 4ia (215.2 mg, 80% yield) (purified by flash column chromatography (eluent:petroleum ether)): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): =7.50 (d, J=8.4 Hz, 2H, ArH), 7.34 (d, J=8.0 Hz, 2H, ArH), 6.12 (dt, J.sub.1=6.3 Hz, J.sub.2=3.1 Hz, 1H, CH), 5.60 (q, J=6.7 Hz, 1H, CH), 2.13 (qd, J.sub.1=7.1 Hz, J.sub.2=3.0 Hz, 2H, CH.sub.2), 1.53-1.41 (m, 2H, CH.sub.2), 1.40-1.21 (m, 6H, CH.sub.23), 0.87 (t, J=6.8 Hz, 3H, CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): =206.2, 139.2, 128.6 (q, J=32.2 Hz), 126.6, 125.4 (q, J=3.8 Hz), 124.4 (q, J=269.9 Hz), 95.7, 93.8, 31.7, 29.1, 28.9, 28.5, 22.7, 14.0; .sup.19F NMR (376 MHz, CDCl.sub.3) =62.9; IR (neat): =2927, 2856, 1950, 1615, 1439, 1322, 1163, 1121, 1064 cm.sup.1; MS (70 eV, EI) m/z (%): 268 (M.sup.+, 1.13), 129 (100).

Example 14

##STR00051##

[0071] The operation is the same as Example 1. 5 molecular sieves (250.1 mg), Au3d (43.7 mg, 0.05 mmol), aldehyde 1j (272.0 mg, 1.8 mmol), 1-methyl-1,2,3,4-tetrahydroisoquinoline 3f (176.5 mg, 1.2 mmol) and terminal alkyne 2f (209.2 mg, 1.0 mmol) were reacted in 2,2,2-trifluoroethanol (1 mL) to afford an allene product 4jf (276.2 mg, 80% yield) (purified by flash column chromatography (eluent:petroleum ether/ethyl acetate=10/1)): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): =8.16 (d, J=9.2 Hz, 2H, ArH), 7.40 (d, J=8.8 Hz, 2H, ArH), 6.27 (dd, J=6.6 Hz, J.sub.2=3.0 Hz, 1H, CH), 5.71 (t, J=6.0 Hz, 1H, CH), 4.27-3.84 (br, 2H, CH.sub.2), 2.82 (t, J=12.2 Hz, 2H, CH.sub.2), 2.42-2.28 (m, 1H, CH), 1.88-1.73 (m, 2H, CH.sub.2), 1.45 (s, 9H, OC(CH.sub.3).sub.3), 1.43-1.29 (m, 2H, CH.sub.2); .sup.13C NMR (100 MHz, CDCl.sub.3): =206.1, 154.6, 146.3, 142.0, 126.8, 123.9, 100.2, 95.1, 79.4, 43.4, 35.4, 31.7, 28.3; IR (neat): =2976, 2932, 2852, 1946, 1680, 1595, 1515, 1421, 1338, 1229, 1164, 1110 cm.sup.1; MS (ESI) m/z (%): 367 (M+Na.sup.+); HRMS Calcd. for C.sub.19H.sub.24O.sub.4N.sub.2Na (M+Na.sup.+): 367.1628, found 367.1623.

Example 15

##STR00052##

[0072] The operation is the same as Example 1. 5 molecular sieves (250.2 mg), Au3d (43.1 mg, 0.05 mmol), aldehyde 1k (417.5 mg, 1.8 mmol), 1-methyl-1,2,3,4-tetrahydroisoquinoline 3f (176.8 mg, 1.2 mmol) and terminal alkyne 2g (80.3 mg, 1.0 mmol) were reacted in 2,2,2-trifluoroethanol (1 mL) to afford an allene product 4 kg (249.2 mg, 84% yield) (purified by flash column chromatography (eluent: petroleum ether/ethyl acetate=200/1)): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): =7.73 (d, J=8.0 Hz, 2H, ArH), 7.28 (d, J=8.0 Hz, 2H, ArH), 6.23-6.06 (m, 1H, CH), 5.94-5.77 (m, 1H, CH), 5.67-5.50 (m, 1H, CH), 5.05 (dd, J.sub.1=17.0 Hz, J.sub.2=1.4 Hz, 1H, one proton of CH.sub.2), 5.00 (d, J=10.0 Hz, 1H, one proton of CH.sub.2), 2.32-2.15 (m, 4H, CH.sub.22), 1.34 (s, 12H, CH.sub.34); .sup.13C NMR (100 MHz, CDCl.sub.3): =205.7, 137.9, 137.8, 135.0, 125.9, 115.2, 95.1, 94.4, 83.6, 33.1, 28.0, 24.81, 24.79; IR (neat): =2977, 2926, 1947, 1607, 1356, 1320, 1142, 1086 cm.sup.1; MS (FI) m/z (%): 296 (M.sup.+(.sup.11B)); HRMS Calcd. for C.sub.19H.sub.25O.sub.2.sup.10B (M.sup.+): 295.1978, found 295.1977.

Example 16

##STR00053##

[0073] The operation is the same as Example 1. 5 molecular sieves (250.6 mg), Au3d (43.5 mg, 0.05 mmol), aldehyde 1k (417.6 mg, 1.8 mmol), 1-methyl-1,2,3,4-tetrahydroisoquinoline 3f (176.9 mg, 1.2 mmol) and terminal alkyne 2h (116.4 mg, 1.0 mmol) were reacted in 2,2,2-trifluoroethanol (1 mL) to afford an allene product 4kh (243.2 mg, 73% yield) (purified by flash column chromatography (eluent:petroleum ether/ethyl acetate=80/1)): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): =7.74 (d, J=7.6 Hz, 2H, ArH), 7.27 (d, J=8.0 Hz, 2H, ArH), 6.15 (dt, J=6.3 Hz, J.sub.2=3.1 Hz, 1H, CH), 5.57 (q, J=6.7 Hz, 1H, CH), 3.53 (t, J=6.6 Hz, 2H, CH.sub.2), 2.17 (qd, J.sub.1=6.9 Hz, J.sub.2=2.8 Hz, 2H, CH.sub.2), 1.91-1.79 (m, 2H, CH.sub.2), 1.70-1.56 (m, 2H, CH.sub.2), 1.34 (s, 12H, CH.sub.34); .sup.13C NMR (100 MHz, CDCl.sub.3): =205.7, 137.7, 135.0, 125.8, 95.1, 94.3, 83.6, 44.6, 31.9, 27.7, 26.1, 24.8, 24.7; IR (neat): =2977, 2935, 1947, 1607, 1356, 1319, 1142, 1086 cm.sup.1; MS (FI) m/z (%): 332 (M.sup.+(.sup.11B, .sup.35Cl)); HRMS Calcd. for C.sub.19H.sub.26O.sub.2.sup.10B.sup.35Cl (M.sup.+): 331.1745, found 331.1751.

Example 17

##STR00054##

[0074] The operation is the same as Example 1. 5 molecular sieves (250.5 mg), Au3d (43.5 mg, 0.05 mmol), aldehyde 1k (418.1 mg, 1.8 mmol), 1-methyl-1,2,3,4-tetrahydroisoquinoline 3f (176.7 mg, 1.2 mmol) and terminal alkyne 2i (133.0 mg, 1.0 mmol) were reacted in 2,2,2-trifluoroethanol (1 mL) to afford an allene product 4ki (199.9 mg, 57% yield) (purified by flash column chromatography (eluent:petroleum ether/ethyl acetate=200/1)): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): =7.74 (d, J=8.0 Hz, 2H, ArH), 7.31 (d, J=7.6 Hz, 2H, ArH), 6.22 (dt, J=6.1 Hz, J.sub.2=3.0 Hz, 1H, CH), 5.62 (q, J=6.7 Hz, 1H, CH), 3.48 (t, J=6.8 Hz, 2H, CH.sub.2), 2.78-2.62 (m, 2H, CH.sub.2), 1.34 (s, 12H, CH.sub.34); .sup.13C NMR (100 MHz, CDCl.sub.3): =206.2, 137.0, 135.0, 126.1, 95.9, 92.5, 83.6, 32.0, 31.6, 24.81, 24.78; IR (neat): =2977, 1949, 1607, 1393, 1356, 1320, 1269, 1142, 1085 cm.sup.1; MS (70 eV, EI) m/z (%): 347 (M.sup.+(.sup.10B, .sup.79Br), 5.98), 348 (M.sup.+(.sup.10B, .sup.79Br), 22.06), 349 (M.sup.+(.sup.10B, .sup.81Br), 9.26), 350 (M.sup.+(.sup.11B, .sup.81Br), 20.95), 169 (100); HRMS Calcd. for C.sub.17H.sub.22O.sub.2.sup.10B.sup.79Br (M.sup.+): 347.0927, found 347.0931.

Example 18

##STR00055##

[0075] The operation is the same as Example 1. 5 molecular sieves (250.6 mg), Au3d (43.5 mg, 0.05 mmol), aldehyde 1k (417.2 mg, 1.8 mmol), 1-methyl-1,2,3,4-tetrahydroisoquinoline 3f (176.4 mg, 1.2 mmol) and terminal alkyne 2j (226.1 mg, 1.0 mmol) were reacted in 2,2,2-trifluoroethanol (1 mL) to afford an allene product 4kj (355.3 mg, 80% yield) (purified by flash column chromatography (eluent:petroleum ether (200 mL); petroleum ether/ethyl acetate=80/1 (405 mL))): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): =7.73 (d, J=8.0 Hz, 2H, ArH), 7.28 (d, J=8.0 Hz, 2H, ArH), 6.12 (dt, J.sub.1=6.3 Hz, J.sub.2=3.1 Hz, 1H, CH), 5.58 (q, J=6.7 Hz, 1H, CH), 3.58 (t, J=6.6 Hz, 2H, OCH.sub.2), 2.14 (qd, J.sub.1=7.0 Hz, J.sub.2=2.9 Hz, 2H, CH.sub.2), 1.57-1.44 (m, 4H, CH.sub.22), 1.44-1.36 (m, 2H, CH.sub.2), 1.34 (s, 12H, CH.sub.34), 0.89 (s, 9H, C(CH.sub.3).sub.3), 0.04 (s, 6H, CH.sub.32); .sup.13C NMR (100 MHz, CDCl.sub.3): =205.7, 138.1, 135.0, 125.9, 95.0, 94.8, 83.6, 63.2, 32.6, 28.9, 28.6, 26.0, 25.4, 24.9, 24.8, 18.4, 5.3; IR (neat): =2931, 2857, 1997, 1608, 1358, 1144, 1088 cm.sup.1; MS (FI) m/z (%): 442 (M.sup.+(.sup.11B)); HRMS Calcd. for C.sub.26H.sub.43O.sub.3Si.sup.10B (M.sup.+): 441.3105, found 441.3108.

Example 19

##STR00056##

[0076] The operation is the same as Example 1. 5 molecular sieves (250.1 mg), Au3d (43.4 mg, 0.05 mmol), aldehyde 1k (417.7 mg, 1.8 mmol), 1-methyl-1,2,3,4-tetrahydroisoquinoline 3f (176.9 mg, 1.2 mmol) and terminal alkyne 2k (112.1 mg, 1.0 mmol) were reacted in 2,2,2-trifluoroethanol (1 mL) to afford an allene product 4kk (258.5 mg, 96% purity, 76% yield) (purified by flash column chromatography (Eluent: petroleum ether/ethyl acetate=10/1)): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): =7.73 (d, J=7.6 Hz, 2H, ArH), 7.28 (d, J=8.0 Hz, 2H, ArH), 6.13 (dt, J.sub.1=6.4 Hz, J.sub.2=3.1 Hz, 1H, CH), 5.58 (q, J=6.5 Hz, 1H, CH), 3.62 (t, J=6.6 Hz, 2H, CH.sub.2), 2.15 (qd, J.sub.1=6.9 Hz, J.sub.2=3.0 Hz, 2H, CH.sub.2), 1.80-1.62 (brs, 1H, OH), 1.62-1.47 (m, 4H, CH.sub.22), 1.47-1.38 (m, 2H, CH.sub.2), 1.34 (s, 12H, CH.sub.34); .sup.13C NMR (100 MHz, CDCl.sub.3): =205.6, 138.0, 134.9, 125.8, 94.8, 94.7, 83.6, 62.6, 32.3, 28.7, 28.4, 25.2, 24.73, 24.70; IR (neat): =3354, 2977, 2931, 2858, 1947, 1607, 1356, 1319, 1142, 1086 cm.sup.1; MS (FI) m/z (%): 328 (M.sup.+(.sup.11B)); HRMS Calcd. for C.sub.20H.sub.29O.sub.3.sup.10B (M.sup.+): 327.2241, found 327.2245.

Example 20

##STR00057##

[0077] The operation is the same as Example 1. 5 molecular sieves (250.1 mg), Au3d (43.4 mg, 0.05 mmol), aldehyde 1k (417.9 mg, 1.8 mmol), 1-methyl-1,2,3,4-tetrahydroisoquinoline 3f (176.7 mg, 1.2 mmol) and terminal alkyne 21 (107.0 mg, 1.0 mmol) were reacted in 2,2,2-trifluoroethanol (1 mL) to afford an allene product 4kl (262.8 mg, 81% yield) (purified by flash column chromatography (eluent:petroleum ether/ethyl acetate=40/1 (410 mL); petroleum ether/ethyl acetate=20/1 (420 mL)): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): =7.74 (d, J=8.0 Hz, 2H, ArH), 7.27 (d, J=8.0 Hz, 2H, ArH), 6.17 (dt, J.sub.1=6.1 Hz, J.sub.2=3.0 Hz, 1H, CH), 5.57 (q, J=6.5 Hz, 1H, CH), 2.33 (t, J=7.0 Hz, 2H, CH.sub.2), 2.18 (qd, J.sub.1=7.0 Hz, J.sub.2=3.0 Hz, 2H, CH.sub.2), 1.80-1.69 (m, 2H, CH.sub.2), 1.69-1.58 (m, 2H, CH.sub.2), 1.34 (s, 12H, CH.sub.34); .sup.13C NMR (100 MHz, CDCl.sub.3): =205.7, 137.6, 135.0, 125.8, 119.5, 95.3, 94.0, 83.7, 27.7, 27.6, 24.81, 24.78, 24.73, 16.9; IR (neat): =2975, 2937, 2896, 1949, 1605, 1355, 1323, 1147, 1089 cm.sup.1; MS (FI) m/z (%): 323 (M.sup.+(.sup.11B)); HRMS Calcd. for C.sub.20H.sub.26O.sub.2N.sup.10B (M.sup.+): 322.2087, found 322.2081.

Example 21

##STR00058##

[0078] The operation is the same as Example 1. 5 molecular sieves (250.1 mg), Au3d (43.7 mg, 0.05 mmol), aldehyde 1k (418.0 mg, 1.8 mmol), 1-methyl-1,2,3,4-tetrahydroisoquinoline 3f (176.5 mg, 1.2 mmol) and terminal alkyne 2m (126.1 mg, 1.0 mmol) were reacted in 2,2,2-trifluoroethanol (1 mL) to afford an allene product 4 km (240.6 mg, 70% yield) (purified by flash column chromatography (eluent:petroleum ether/ethyl acetate=80/1 (405 mL); petroleum ether/ethyl acetate=40/1 (820 mL)): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): =7.73 (d, J=8.0 Hz, 2H, ArH), 7.27 (d, J=9.2 Hz, 2H, ArH), 6.16 (dt, J.sub.1=6.1 Hz, J.sub.2=3.0 Hz, 1H, CH), 5.57 (q, J=6.7 Hz, 1H, CH), 3.66 (s, 3H, OCH.sub.3), 2.39 (t, J=7.6 Hz, 2H, CH.sub.2), 2.25-2.12 (m, 2H, CH.sub.2), 1.89-1.75 (m, 2H, CH.sub.2), 1.34 (s, 12H, CH.sub.34); .sup.13C NMR (100 MHz, CDCl.sub.3): =205.8, 173.8, 137.7, 135.0, 125.9, 95.2, 94.1, 83.6, 51.4, 33.3, 27.9, 24.80, 24.77, 24.1; IR (neat): =2977, 1947, 1737, 1607, 1356, 1142, 1086 cm.sup.1; MS (FI) m/z (%): 342 (M.sup.+(.sup.11B)); HRMS Calcd. for C.sub.20H.sub.27O.sub.4.sup.10B (M.sup.+): 341.2033, found 341.2039.

Example 22

##STR00059##

[0079] The operation is the same as Example 1. 5 molecular sieves (12.5025 g), Au3d (1.0851 g, 1.25 mmol), aldehyde 1k (20.8894 g, 90 mmol), 1-methyl-1,2,3,4-tetrahydroisoquinoline 3f (8.8317 g, 60 mmol) and terminal alkyne 2m (6.3093 g, 50 mmol) were reacted in 2,2,2-trifluoroethanol (50 mL) to afford an allene product 4 km (10.9863 g, 64% yield) (purified by flash column chromatography (eluent:petroleum ether/ethyl acetate=40/1)): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): =7.73 (d, J=8.0 Hz, 2H, ArH), 7.27 (d, J=9.2 Hz, 2H, ArH), 6.16 (dt, J=6.1 Hz, J.sub.2=3.0 Hz, 1H, CH), 5.57 (q, J=6.7 Hz, 1H, CH), 3.66 (s, 3H, OCH.sub.3), 2.39 (t, J=7.4 Hz, 2H, CH.sub.2), 2.18 (qd, J.sub.1=6.9 Hz, J.sub.2=2.9 Hz, 2H, CH.sub.2), 1.89-1.74 (m, 2H, CH.sub.2), 1.34 (s, 12H, CH.sub.34).

Example 23

##STR00060##

[0080] The operation is the same as Example 1. 5 molecular sieves (250.4 mg), Au3d (43.5 mg, 0.05 mmol), aldehyde 11 (263.5 mg, 1.8 mmol), 1-methyl-1,2,3,4-tetrahydroisoquinoline 3f (177.1 mg, 1.2 mmol) and terminal alkyne 2n (96.0 mg, 1.0 mmol) were reacted in 2,2,2-trifluoroethanol (1 mL) to afford an allene product 4ln (208.9 mg, 93% yield) (purified by flash column chromatography (eluent:petroleum ether)): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): =7.59 (d, J=2.4 Hz, 1H, ArH), 7.48 (s, 1H, ArH), 7.42 (d, J=8.8 Hz, 1H, ArH), 7.31-7.22 (m, 1H, ArH), 6.75-6.68 (m, 1H, ArH), 6.22 (dt, J.sub.1=6.3 Hz, J.sub.2=3.1 Hz, 1H, CH), 5.58 (q, J=6.7 Hz, 1H, CH), 2.14 (qd, J.sub.1=7.1 Hz, J.sub.2=2.9 Hz, 2H, CH.sub.2), 1.54-1.43 (m, 2H, CH.sub.2), 1.42-1.23 (m, 4H, CH.sub.22), 0.89 (t, J=7.0 Hz, 3H, CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): =204.7, 154.1, 145.2, 129.9, 127.8, 123.1, 118.9, 111.3, 106.4, 95.1, 94.6, 31.4, 28.8, 22.4, 14.0; IR (neat): =2925, 2855, 1948, 1466, 1452, 1262, 1192, 1111, 1031 cm.sup.1; MS (70 eV, EI) m/z (%): 226 (M.sup.+, 12.48), 170 (100); HRMS Calcd. for C.sub.16H.sub.18O (M.sup.+): 226.1352, found 226.1356.

Example 24

##STR00061##

[0081] The operation is the same as Example 1. 5 molecular sieves (250.4 mg), Au3d (43.1 mg, 0.05 mmol), aldehyde 1m (193.1 mg, 1.8 mmol), 1-methyl-1,2,3,4-tetrahydroisoquinoline 3f (176.5 mg, 1.2 mmol) and terminal alkyne 2n (96.0 mg, 1.0 mmol) were reacted in 2,2,2-trifluoroethanol (1 mL) to afford an allene product 4mn (152.3 mg, 81% yield) (purified by flash column chromatography (eluent:petroleum ether/ethyl acetate=20/1)): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): =8.51 (d, J=1.6 Hz, 1H, ArH), 8.41 (dd, J.sub.1=4.8 Hz, J.sub.2=1.2 Hz, 1H, ArH), 7.58 (dt, J.sub.1=7.6 Hz, J.sub.2=1.6 Hz, 1H, ArH), 7.21 (dd, J.sub.1=7.6 Hz, J.sub.2=4.8 Hz, 1H, ArH), 6.10 (dt, J.sub.1=6.4 Hz, J.sub.2=3.2 Hz, 1H, CH), 5.63 (q, J=6.7 Hz, 1H, CH), 2.14 (qd, J.sub.1=7.2 Hz, J.sub.2=3.1 Hz, 2H, CH.sub.2), 1.57-1.41 (m, 2H, CH.sub.2), 1.40-1.22 (m, 4H, CH.sub.22), 0.89 (t, J=7.0 Hz, 3H, CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): =205.4, 147.9, 147.5, 133.1, 130.9, 123.2, 95.6, 91.2, 31.2, 28.6, 28.3, 22.3, 13.9; IR (neat): =2925, 2855, 1949, 1570, 1480, 1444, 1390, 1180, 1120, 1023 cm.sup.1; MS (70 eV, EI) m/z (%): 187 (M.sup.+, 1.42), 130 (100); HRMS Calcd. for C.sub.13H.sub.17N (M.sup.+): 187.1356, found 187.1359.

Example 25

##STR00062##

[0082] The operation is the same as Example 1. 5 molecular sieves (250.2 mg), Au3d (43.5 mg, 0.05 mmol), aldehyde in (173.4 mg, 1.8 mmol), 1-methyl-1,2,3,4-tetrahydroisoquinoline 3f (176.5 mg, 1.2 mmol) and terminal alkyne 2n (96.3 mg, 1.0 mmol) were reacted in 2,2,2-trifluoroethanol (1 mL) to afford an allene product 4nn (63.8 mg, 36% yield) (purified by flash column chromatography (eluent:petroleum ether)): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): =7.38-7.31 (m, 1H, ArH), 6.37 (dd, J.sub.1=3.2 Hz, J.sub.2=2.0 Hz, 1H, ArH), 6.18 (d, J=3.2 Hz, 1H, ArH), 6.10 (dt, J.sub.1=6.3 Hz, J.sub.2=3.1 Hz, 1H, CH), 5.60 (q, J=6.8 Hz, 1H, CH), 2.12 (qd, J.sub.1=7.1 Hz, J.sub.2=3.0 Hz, 2H, CH.sub.2), 1.53-1.42 (m, 2H, CH.sub.2), 1.40-1.22 (m, 4H, CH.sub.22), 0.89 (t, J=7.0 Hz, 3H, CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): =204.4, 149.0, 141.7, 111.3, 106.5, 95.6, 85.3, 31.3, 28.8, 28.5, 22.4, 14.0; IR (neat): =2926, 2856, 1950, 1462, 1249, 1174, 1150, 1076, 1010 cm.sup.1; MS (70 eV, EI) m/z (%): 176 (M.sup.+, 11.56), 120 (100); HRMS Calcd. for C.sub.12H.sub.16O (M.sup.+): 176.1196, found 176.1200.

Example 26

##STR00063##

[0083] The operation is the same as Example 1. 5 molecular sieves (250.5 mg), Au3d (43.4 mg, 0.05 mmol), aldehyde to (201.7 mg, 1.8 mmol), 1-methyl-1,2,3,4-tetrahydroisoquinoline 3f (176.6 mg, 1.2 mmol) and terminal alkyne 2n (96.3 mg, 1.0 mmol) were reacted in 2,2,2-trifluoroethanol (1 mL) to afford an allene product 4on (154.0 mg, 80% yield) (purified by flash column chromatography (eluent:petroleum ether)): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): =7.24 (dd, J.sub.1=5.2 Hz, J.sub.2=2.8 Hz, 1H, ArH), 7.06 (d, J=4.8 Hz, 1H, ArH), 7.03 (d, J=2.8 Hz, 1H, ArH), 6.18 (dt, J.sub.1=6.1 Hz, J.sub.2=3.1 Hz, 1H, CH), 5.49 (q, J=6.5 Hz, 1H, CH), 2.10 (qd, J.sub.1=7.1 Hz, J.sub.2=3.0 Hz, 2H, CH.sub.2), 1.52-1.42 (m, 2H, CH.sub.2), 1.39-1.24 (m, 4H, CH.sub.22), 0.89 (t, J=7.0 Hz, 3H, CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): =205.4, 136.5, 126.2, 125.6, 120.0, 94.2, 89.1, 31.3, 28.78, 28.77, 22.4, 14.0; IR (neat): =2924, 2854, 1950, 1462, 1378, 1261, 1232, 1077 cm.sup.1; MS (70 eV, EI) m/z (%): 192 (M.sup.+, 5.72), 135 (100); HRMS Calcd. for C.sub.12H.sub.16S (M.sup.+): 192.0967, found 192.0966.

Example 27

##STR00064##

[0084] The operation is the same as Example 1. 5 molecular sieves (250.6 mg), Au3d (43.5 mg, 0.05 mmol), aldehyde 1p (263.4 mg, 1.8 mmol), 1-methyl-1,2,3,4-tetrahydroisoquinoline 3f (176.5 mg, 1.2 mmol) and terminal alkyne 2o (108.3 mg, 1.0 mmol) were reacted in 2,2,2-trifluoroethanol (1 mL) to afford an allene product 4po (203.0 mg, 85% yield) (purified by flash column chromatography (eluent:petroleum ether/ethyl acetate=4/1)): white solid; m.p. 152.0-152.9 C. (recrystallized from ethyl acetate); .sup.1H NMR (400 MHz, CDCl.sub.3): =10.80-10.04 (brs, 1H, NH), 8.03 (s, 1H, ArH), 7.59 (s, 1H, ArH), 7.43 (s, 2H, ArH), 6.28 (dd, J.sub.1=6.4 Hz, J.sub.2=2.8 Hz, 1H, CH), 5.60 (t, J=6.0 Hz, 1H, CH), 2.23-2.04 (m, 1H, CH), 1.94-1.82 (m, 2H), 1.82-1.68 (m, 2H), 1.68-1.57 (m, 1H), 1.40-1.08 (m, 5H); .sup.13C NMR (100 MHz, CDCl.sub.3): =203.7, 139.4, 134.7, 128.4, 126.0, 123.7, 118.1, 109.9, 101.2, 95.5, 37.7, 33.2, 33.1, 26.1, 26.02, 26.01; IR (neat): =3139, 2918, 2848, 1946, 1623, 1506, 1442, 1341, 1307, 1081 cm.sup.1; MS (ESI) m/z (%): 239 (M+H.sup.+); Anal. Calcd. for C.sub.16H.sub.18N.sub.2: C 80.63, H, 7.61, N 11.75, found C 80.49, H 7.69, N 11.72.

Example 28

##STR00065##

[0085] The operation is the same as Example 1. 5 molecular sieves (250.2 mg), Au3d (43.1 mg, 0.05 mmol), aldehyde 1q (261.0 mg, 1.8 mmol), 1-methyl-1,2,3,4-tetrahydroisoquinoline 3f (176.4 mg, 1.2 mmol) and terminal alkyne 2o (107.8 mg, 1.0 mmol) were reacted in 2,2,2-trifluoroethanol (1 mL) to afford an allene product 4qo (133.6 mg, 57% yield) (purified by flash column chromatography (eluent:petroleum ether/ethyl acetate=40/1)): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): =8.22-7.85 (brs, 1H, NH), 7.52 (s, 1H, ArH), 7.29 (d, J=8.4 Hz, 1H, ArH), 7.22 (t, J=7.6 Hz, 1H, ArH) 7.13 (s, 1H, ArH), 6.49 (s, 1H, ArH), 6.28 (dd, J.sub.1=6.0 Hz, J.sub.2=2.8 Hz, 1H, CH), 5.56 (t, J=6.2 Hz, 1H, CH), 2.22-2.05 (m, 1H, CH), 1.95-1.80 (m, 2H), 1.80-1.68 (m, 2H), 1.68-1.58 (m, 1H), 1.38-1.08 (m, 5H); .sup.13C NMR (100 MHz, CDCl.sub.3): =203.3, 134.9, 128.1, 126.7, 124.5, 120.9, 118.5, 111.2, 102.4, 100.8, 96.1, 37.7, 33.2, 33.1, 26.1, 26.03, 26.02; IR (neat): =3410, 2921, 2848, 1945, 1447, 1415, 1319, 1285, 1091 cm.sup.1; MS (ESI) m/z (%): 238 (M+H.sup.+); HRMS Calcd. for C.sub.17H.sub.20N (M+H.sup.+): 238.1590, found 238.1588.

Example 29

##STR00066##

[0086] The operation is the same as Example 1. 5 molecular sieves (250.4 mg), Au3d (43.7 mg, 0.05 mmol), aldehyde 1r (281.5 mg, 1.8 mmol), 1-methyl-1,2,3,4-tetrahydroisoquinoline 3f (176.4 mg, 1.2 mmol) and terminal alkyne 2g (80.0 mg, 1.0 mmol) were reacted in 2,2,2-trifluoroethanol (1 mL) to afford an allene product 4rg (145.7 mg, 66% yield) (purified by flash column chromatography (eluent: petroleum ether)): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): =7.82-7.70 (m, 3H, ArH), 7.64 (s, 1H, ArH), 7.53-7.47 (m, 1H, ArH), 7.47-7.36 (m, 2H, ArH), 6.37-6.26 (m, 1H, CH), 5.96-5.78 (m, 1H, CH), 5.65 (q, J=6.1 Hz, 1H, CH), 5.08 (d, J=17.6 Hz, 1H, one proton of CH.sub.2), 5.02 (d, J=10.0 Hz, 1H, one proton of CH.sub.2), 2.36-2.17 (m, 4H, CH.sub.22); .sup.13C NMR (100 MHz, CDCl.sub.3): =205.7, 137.8, 133.7, 132.5, 132.4, 128.1, 127.63, 127.58, 126.1, 125.4, 125.3, 124.6, 115.2, 95.3, 94.6, 33.1, 28.1; IR (neat): =3054, 2976, 2909, 2843, 1945, 1639, 1597, 1507, 1435, 1264 cm.sup.1; MS (70 eV, EI) m/z (%): 220 (M.sup.+, 91.99), 178 (100); HRMS Calcd. for C.sub.17H.sub.16 (M.sup.+): 220.1247, found 220.1248.

Example 30

##STR00067##

[0087] The operation is the same as Example 1. 5 molecular sieves (250.4 mg), Au3d (43.5 mg, 0.05 mmol), aldehyde is (371.4 mg, 1.8 mmol), 1-methyl-1,2,3,4-tetrahydroisoquinoline 3f (176.8 mg, 1.2 mmol) and terminal alkyne 2g (80.1 mg, 1.0 mmol) were reacted in 2,2,2-trifluoroethanol (1 mL) to afford an allene product 4sg (139.9 mg, 52% yield) (purified by flash column chromatography (eluent: petroleum ether)): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): =8.74-8.66 (m, 1H, ArH), 8.62 (d, J=8.0 Hz, 1H, ArH), 8.36-8.27 (m, 1H, ArH), 7.87-7.81 (m, 1H, ArH), 7.78 (s, 1H, ArH), 7.69-7.48 (m, 4H, ArH), 6.87-6.78 (m, 1H, CH), 5.96-5.80 (m, 1H, CH), 5.64 (q, J=6.5 Hz, 1H, CH), 5.08 (d, J=17.2 Hz, 1H, one proton of CH.sub.2), 5.01 (d, J=10.0 Hz, 1H, one proton of CH.sub.2), 2.39-2.22 (m, 4H, CH.sub.22); .sup.13C NMR (100 MHz, CDCl.sub.3): =206.7, 137.9, 131.8, 130.7, 130.2, 129.8, 129.6, 128.3, 126.7, 126.5, 126.34, 126.28, 125.9, 124.4, 123.1, 122.5, 115.3, 93.2, 91.7, 33.2, 28.2; IR (neat): =3073, 2973, 2909, 2844, 1946, 1639, 1494, 1428, 1243, 1114 cm.sup.1; MS (70 eV, EI) m/z (%): 270 (M.sup.+, 100); HRMS Calcd. for C.sub.21H.sub.18 (M.sup.+): 270.1403, found 270.1408.

Example 31

##STR00068##

[0088] The operation is the same as Example 1. 5 molecular sieves (250.2 mg), Au3d (43.4 mg, 0.05 mmol), aldehyde it (414.6 mg, 1.8 mmol), 1-methyl-1,2,3,4-tetrahydroisoquinoline 3f (176.8 mg, 1.2 mmol) and terminal alkyne 2g (79.8 mg, 1.0 mmol) were reacted in 2,2,2-trifluoroethanol (1 mL) to afford an allene product 4tg (151.6 mg, 52% yield) (purified by flash column chromatography (eluent: petroleum ether)): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): =8.40 (d, J=9.2 Hz, 1H, ArH), 8.18-8.04 (m, 5H, ArH), 8.04-7.94 (m, 3H, ArH), 7.23-7.10 (m, 1H, CH), 5.98-5.83 (m, 1H, CH), 5.75 (q, J=6.1 Hz, 1H, CH), 5.10 (d, J=16.8 Hz, 1H, one proton of CH.sub.2), 5.03 (d, J=10.8 Hz, 1H, one proton of CH.sub.2), 2.43-2.24 (m, 4H, CH.sub.22); .sup.13C NMR (100 MHz, CDCl.sub.3): =207.2, 137.9, 131.4, 130.8, 130.1, 128.5, 127.5, 127.4, 127.3, 126.9, 125.8, 125.2, 125.1, 125.04, 124.96, 124.9, 124.7, 122.7, 115.3, 94.0, 92.0, 33.3, 28.2; IR (neat): =3040, 2973, 2906, 2842, 1941, 1639, 1599, 1435, 1269, 1182 cm.sup.1; MS (70 eV, EI) m/z (%): 294 (M.sup.+, 94.55), 253 (100); HRMS Calcd. for C.sub.23H.sub.18 (M.sup.+): 294.1403, found 294.1407.

Example 32

##STR00069##

[0089] The operation is the same as Example 1. 5 molecular sieves (250.4 mg), Au3d (43.5 mg, 0.05 mmol), aldehyde 1u (256.5 mg, 1.8 mmol), 1-methyl-1,2,3,4-tetrahydroisoquinoline 3f (176.6 mg, 1.2 mmol) and terminal alkyne 2a (110.2 mg, 1.0 mmol) were reacted in 2,2,2-trifluoroethanol (5 mL) to afford an allene product 4ua (195.7 mg, 83% yield) (purified by flash column chromatography (eluent:petroleum ether)): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): =5.06 (quintet, J=4.8 Hz, 2H, CH2), 2.07-1.86 (m, 4H, CH.sub.22), 1.48-1.13 (m, 20H, CH.sub.210), 0.96-0.77 (m, 6H, CH.sub.32); .sup.13C NMR (150 MHz, CDCl.sub.3): =204.0, 90.87, 90.86, 32.0, 31.8, 29.6, 29.4, 29.32, 29.28, 29.2, 29.084, 29.078, 28.9, 22.75, 22.73, 14.09, 14.08; IR (neat): =2957, 2922, 2853, 1963, 1462, 1378, 1261 cm.sup.1; MS (FI) m z (%): 236 (M.sup.+); HRMS Calcd. for C.sub.17H.sub.32 (M.sup.+): 236.2499, found 236.2500.

Example 33

##STR00070##

[0090] The operation is the same as Example 1. 5 molecular sieves (250.2 mg), Au3d (43.3 mg, 0.05 mmol), aldehyde 1v (180.5 mg, 1.8 mmol), 1-methyl-1,2,3,4-tetrahydroisoquinoline 3f (176.8 mg, 1.2 mmol) and terminal alkyne 2a (110.2 mg, 1.0 mmol) were reacted in 2,2,2-trifluoroethanol (5 mL) to afford an allene product 4va (126.1 mg, 65% yield) (purified by flash column chromatography (eluent:petroleum ether)): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): =5.06 (quintet, J=4.8 Hz, 2H, CH2), 2.06-1.86 (m, 4H, CH.sub.22), 1.48-1.16 (m, 14H, CH.sub.27), 0.97-0.74 (m, 6H, CH.sub.32); .sup.13C NMR (100 MHz, CDCl.sub.3): =203.8, 90.9, 31.8, 31.4, 29.2, 29.04, 29.00, 28.9, 28.8, 22.7, 22.5, 14.08, 14.07; IR (neat): =2957, 2924, 2855, 1962, 1462, 1378, 1261, 1104, 1018 cm.sup.1; MS (FI) m/z (%): 194 (M.sup.+); HRMS Calcd. for C.sub.14H.sub.26 (M.sup.+): 194.2029, found 194.2032.

Example 34

##STR00071##

[0091] The operation is the same as Example 1. 5 molecular sieves (250.2 mg), Au3d (43.5 mg, 0.05 mmol), aldehyde 1w (155.3 mg, 1.8 mmol), 1-methyl-1,2,3,4-tetrahydroisoquinoline 3f (176.2 mg, 1.2 mmol) and terminal alkyne 2a (110.2 mg, 1.0 mmol) were reacted in 2,2,2-trifluoroethanol (5 mL) to afford an allene product 4wa (148.0 mg, 82% yield) (purified by flash column chromatography (eluent:petroleum ether)): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): =5.11-4.94 (m, 2H, CH2), 2.02-1.92 (m, 2H, CH.sub.2), 1.92-1.78 (m, 2H, CH.sub.2), 1.72-1.58 (m, 1H, CH), 1.43-1.19 (m, 8H, CH.sub.24), 1.02-0.78 (m, 9H, CH.sub.33); .sup.13C NMR (100 MHz, CDCl.sub.3): =204.5, 90.2, 89.4, 38.6, 31.7, 29.2, 29.0, 28.8, 28.5, 22.7, 22.3, 22.2, 14.1; IR (neat): =2956, 2925, 2855, 1963, 1464, 1381, 1366, 1261, 1105 cm.sup.1; MS (FI) m z (%): 180 (M.sup.+); HRMS Calcd. for C.sub.13H.sub.24 (M.sup.+): 180.1873, found 180.1875.

Example 35

##STR00072##

[0092] The operation is the same as Example 1. 5 molecular sieves (250.1 mg), Au3d (43.5 mg, 0.05 mmol), aldehyde 1x (202.5 mg, 1.8 mmol), 1-methyl-1,2,3,4-tetrahydroisoquinoline 3f (176.3 mg, 1.2 mmol) and the terminal alkyne 2a (110.0 mg, 1.0 mmol) were reacted in 2,2,2-trifluoroethanol (2 mL) to afford an allene product 4xa (161.2 mg, 78% yield) (purified by flash column chromatography (eluent:petroleum ether)): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): =5.20-4.97 (m, 2H, CH2), 2.06-1.86 (m, 3H, CH.sub.2 and CH), 1.82-1.67 (m, 4H), 1.67-1.58 (m, 1H), 1.46-1.00 (m, 13H), 0.89 (t, J=6.8 Hz, 3H, CH.sub.3); .sup.13C NMR (150 MHz, CDCl.sub.3): =202.7, 97.0, 91.8, 37.3, 33.18, 33.15, 31.7, 29.2, 29.1, 28.9, 26.2, 26.10, 26.09, 22.7, 14.1; IR (neat): =2922, 2851, 1960, 1448, 1260 cm.sup.1; MS (70 eV, EI) m/z (%): 206 (M.sup.+, 2.43), 136 (100); HRMS Calcd. for C.sub.15H.sub.26 (M.sup.+): 206.2029, found 206.2032.

Example 36

##STR00073##

[0093] The operation is the same as Example 1. 5 molecular sieves (250.5 mg), Au3d (43.4 mg, 0.05 mmol), aldehyde 1u (256.1 mg, 1.8 mmol), 1-methyl-1,2,3,4-tetrahydroisoquinoline 3f (176.9 mg, 1.2 mmol) and terminal alkyne 2e (102.0 mg, 1.0 mmol) were reacted in 2,2,2-trifluoroethanol (5 mL) to afford an allene product 4ue (161.1 mg, 70% yield, 99% purity) (purified by flash column chromatography (Eluant:petroleum ether)): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): =7.36-7.26 (m, 4H, ArH), 7.22-7.13 (m, 1H, ArH), 6.12 (dt, J.sub.1=6.0 Hz, J.sub.2=2.9 Hz, 1H, CH), 5.56 (q, J=6.7 Hz, 1H, CH), 2.12 (qd, J.sub.1=7.1 Hz, J.sub.2=2.7 Hz, 2H, CH.sub.2), 1.53-1.41 (m, 2H, CH.sub.2), 1.41-1.11 (m, 10H, CH.sub.25), 0.88 (t, J=6.6 Hz, 3H, CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): =205.1, 135.1, 128.5, 126.54, 126.52, 95.1, 94.5, 31.8, 29.4, 29.3, 29.2, 29.1, 28.7, 22.7, 14.1; IR (neat): =2923, 2853, 1949, 1598, 1494, 1459 cm.sup.1; MS (FI) m/z (%): 228 (M.sup.+); HRMS Calcd. for C.sub.17H.sub.24 (M.sup.+): 228.1873, found 228.1869.

Example 37

##STR00074##

[0094] The operation is the same as Example 1. 5 molecular sieves (250.0 mg), Au3d (43.4 mg, 0.05 mmol), aldehyde 1x (202.5 mg, 1.8 mmol), 1-methyl-1,2,3,4-tetrahydroisoquinoline 3f (176.3 mg, 1.2 mmol) and terminal alkyne 2e (102.0 mg, 1.0 mmol) were reacted in 2,2,2-trifluoroethanol (2 mL) to afford an allene product 4xe (145.4 mg, 73% yield) (purified by flash column chromatography (eluent:petroleum ether)): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): =7.36-7.26 (m, 4H, ArH), 7.22-7.11 (m, 1H, ArH), 6.15 (dd, J.sub.1=6.2 Hz, J.sub.2=3.0 Hz, 1H, CH), 5.56 (t, J=6.2 Hz, 1H, CH), 2.18-2.04 (m, 1H, CH), 1.92-1.78 (m, 2H), 1.78-1.68 (m, 2H), 1.68-1.57 (m, 1H), 1.37-1.08 (m, 5H); .sup.13C NMR (100 MHz, CDCl.sub.3): =204.0, 135.2, 128.5, 126.5, 126.4, 101.0, 95.4, 37.6, 33.15, 33.09, 26.09, 26.08, 26.02; IR (neat): =2921, 2849, 1946, 1597, 1493, 1446 cm.sup.1; MS (70 eV, EI) m/z (%): 198 (M.sup.+, 5.19), 105 (100).

Example 38

##STR00075##

[0095] The operation is the same as Example 1. 5 molecular sieves (250.2 mg), Au3d (43.4 mg, 0.05 mmol), aldehyde 1c (253.4 mg, 1.8 mmol), 1-methyl-1,2,3,4-tetrahydroisoquinoline 3f (176.7 mg, 1.2 mmol) and terminal alkyne 2q (138.1 mg, 1.0 mmol) were reacted in 2,2,2-trifluoroethanol (1 mL) to afford an allene product 4cq (200.1 mg, 76% yield) (purified by flash column chromatography (eluent:petroleum ether)): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): =7.28-7.22 (m, 2H, ArH), 7.22-7.16 (m, 2H, ArH), 6.07 (dt, J.sub.1=6.3 Hz, J.sub.2=3.1 Hz, 1H, CH), 5.57 (q, J=6.7 Hz, 1H, CH), 2.12 (qd, J.sub.1=7.1 Hz, J.sub.2=2.9 Hz, 2H, CH.sub.2), 1.53-1.41 (m, 2H, CH.sub.2), 1.41-1.14 (m, 10H, CH.sub.25), 0.87 (t, J=6.8 Hz, 3H, CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): =205.2, 133.7, 132.1, 128.6, 127.7, 95.5, 93.7, 31.8, 29.4, 29.3, 29.2, 29.1, 28.6, 22.7, 14.1; IR (neat): =2923, 2853, 1949, 1490, 1463, 1090, 1013 cm.sup.1; MS (70 eV, EI) m/z (%): 264 (M.sup.+(.sup.37Cl), 0.63), 262 (M.sup.+(.sup.35Cl), 2.02), 129 (100).

Example 39

##STR00076##

[0096] The operation is the same as Example 1. 5 molecular sieves (250.2 mg), Au3d (43.3 mg, 0.05 mmol), aldehyde 1d (333.5 mg, 1.8 mmol), 1-methyl-1,2,3,4-tetrahydroisoquinoline 3f (176.6 mg, 1.2 mmol) and terminal alkyne 2q (138.1 mg, 1.0 mmol) were reacted in 2,2,2-trifluoroethanol (1 mL) to afford an allene product 4dq (230.9 mg, 75% yield) (purified by flash column chromatography (eluent:petroleum ether)): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): =7.40 (d, J=8.4 Hz, 2H, ArH), 7.14 (d, J=8.4 Hz, 2H, ArH), 6.06 (dt, J.sub.1=6.3 Hz, J.sub.2=3.1 Hz, 1H, CH), 5.56 (q, J=6.5 Hz, 1H, CH), 2.12 (qd, J.sub.1=7.1 Hz, J.sub.2=2.9 Hz, 2H, CH.sub.2), 1.53-1.40 (m, 2H, CH.sub.2), 1.40-1.14 (m, 10H, CH.sub.25), 0.88 (t, J=6.8 Hz, 3H, CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): =205.2, 134.2, 131.5, 128.0, 120.1, 95.5, 93.8, 31.8, 29.4, 29.3, 29.2, 29.1, 28.6, 22.7, 14.1; IR (neat): =2922, 2852, 1949, 1486, 1462, 1069, 1009 cm.sup.1; MS (70 eV, EI) m/z (%): 308 (M.sup.+(.sup.81Br), 3.73), 306 (M.sup.+(.sup.79Br), 4.13), 210 (100).

Example 40

##STR00077##

[0097] The operation is the same as Example 1. 5 molecular sieves (250.6 mg), Au3d (43.4 mg, 0.05 mmol), aldehyde 1i (313.2 mg, 1.8 mmol), 1-methyl-1,2,3,4-tetrahydroisoquinoline 3f (176.3 mg, 1.2 mmol) and terminal alkyne 2b (166.3 mg, 1.0 mmol) were reacted in 2,2,2-trifluoroethanol (1 mL) to afford an allene product 4ib (253.8 mg, 78% yield) (purified by flash column chromatography (eluent:petroleum ether)): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): =7.53 (d, J=8.0 Hz, 2H, ArH), 7.37 (d, J=8.0 Hz, 2H, ArH), 6.14 (dt, J.sub.1=6.1 Hz, J.sub.2=3.0 Hz, 1H, CH), 5.63 (q, J=6.7 Hz, 1H, CH), 2.14 (qd, J.sub.1=7.1 Hz, J.sub.2=3.1 Hz, 2H, CH.sub.2), 1.53-1.41 (m, 2H, CH.sub.2), 1.41-1.12 (m, 14H, CH.sub.27), 0.88 (t, J=6.8 Hz, 3H, CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): =206.2, 139.2, 128.6 (q, J=32.2 Hz), 126.6, 125.4 (q, J=3.8 Hz), 124.4 (q, J=269.6 Hz), 95.7, 93.8, 32.0, 29.71, 29.67, 29.5, 29.4, 29.2, 29.1, 28.5, 22.7, 14.1; .sup.19F NMR (376 MHz, CDCl.sub.3) =62.9; IR (neat): =2924, 2854, 1949, 1616, 1322, 1163, 1123, 1065 cm.sup.1; MS (70 eV, EI) m/z (%): 324 (M.sup.+, 2.97), 198 (100).

Example 41

##STR00078##

[0098] The operation is the same as Example 1. 5 molecular sieves (250.3 mg), Au3d (43.4 mg, 0.05 mmol), aldehyde to (202.1 mg, 1.8 mmol), 1-methyl-1,2,3,4-tetrahydroisoquinoline 3f (176.8 mg, 1.2 mmol) and terminal alkyne 2q (138.2 mg, 1.0 mmol) were reacted in 2,2,2-trifluoroethanol (1 mL) to afford an allene product 4oq (201.5 mg, 86% yield) (purified by flash column chromatography (eluent:Petroleum ether)): Oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): =7.27-7.21 (m, 1H, ArH), 7.06 (d, J=5.2 Hz, 1H, ArH), 7.04-6.99 (m, 1H, ArH), 6.18 (dt, J.sub.1=6.3 Hz, J.sub.2=3.0 Hz, 1H, CH), 5.48 (q, J=6.7 Hz, 1H, CH), 2.10 (qd, J.sub.1=7.0 Hz, J.sub.2=3.0 Hz, 2H, CH.sub.2), 1.52-1.42 (m, 2H, CH.sub.2), 1.40-1.12 (m, 10H, CH.sub.25), 0.88 (t, J=6.6 Hz, 3H, CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): =205.4, 136.5, 126.2, 125.6, 120.0, 94.2, 89.1, 31.8, 29.4, 29.3, 29.2, 29.1, 28.8, 22.7, 14.1; IR (neat): =2922, 2852, 1950, 1461, 1378, 1233 cm.sup.1; MS (70 eV, EI) m/z (%): 234 (M.sup.+, 1.95), 135 (100).

Example 42

##STR00079##

[0099] Lithium hydroxide (18.0 mg, 0.75 mmol), allene 4 km (171.3 mg, 0.5 mmol), ethanol (2.5 mL) and water (2.5 mL) were added in sequence to a reaction flask. After the reaction bottle was put into an oil bath at 90 C. to react for 14 hours, water (2 mL) and aqueous hydrochloric acid (1 M, 2 mL) were added in sequence to the reaction bottle. The mixture was extracted with ether (4 mL5). The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and concentrated to afford a product 6 (151.9 mg, 93% purity, 86% yield): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): =12.00-8.60 (br, 1H, CO.sub.2H), 7.74 (d, J=8.0 Hz, 2H, ArH), 7.27 (d, J=7.6 Hz, 2H, ArH), 6.17 (dt, J.sub.1=5.9 Hz, J.sub.2=2.9 Hz, 1H, CH), 5.57 (q, J=6.5 Hz, 1H, CH), 2.43 (t, J=7.4 Hz, 2H, CH.sub.2), 2.20 (qd, J.sub.1=7.1 Hz, J.sub.2=3.0 Hz, 2H, CH.sub.2), 1.90-1.75 (m, 2H, CH.sub.2), 1.34 (s, 12H, CH.sub.34); .sup.13C NMR (100 MHz, CDCl.sub.3): =205.8, 179.8, 137.7, 135.0, 125.9, 95.3, 94.0, 83.7, 33.3, 27.8, 24.78, 24.75, 23.8; IR (neat): =2976, 1944, 1701, 1607, 1355, 1321, 1245, 1168, 1140, 1088 cm.sup.1; MS (FI) m/z (%): 328 (M.sup.+(.sup.11B)); HRMS Calcd. for C.sub.19H.sub.25O.sub.4.sup.10B (M.sup.+): 327.1877, found 327.1882.

Example 43

##STR00080##

[0100] Au(SIPr)Cl (6.2 mg, 0.01 mmol), AgOTs (2.9 mg, 0.01 mmol) and chloroform (2 mL) were added in sequence to a reaction flask. After stirring at room temperature for 15 minutes, 6 (70.1 mg, 93% purity, 0.2 mmol) and chloroform (1 mL) were added in sequence. After stirring at room temperature for 36 hours, the reaction solution was filtered through a short silica gel column, and the filter cake was washed with ethyl acetate (30 mL), concentrated, purified by flash column chromatography (eluent:petroleum ether/ethyl acetate=4/1) to afford a product (E)-6 (47.9 mg, 73% yield): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): =7.77 (d, J=8.0 Hz, 2H, ArH), 7.39 (d, J=8.0 Hz, 2H, ArH), 6.68 (d, J=16.0 Hz, 1H, CH), 6.27 (dd, J.sub.1=15.8 Hz, J.sub.2=6.2 Hz, 1H, CH), 5.09-4.91 (m, 1H, OCH), 2.73-2.58 (m, 1H, one proton of CH.sub.2), 2.58-2.46 (m, 1H, one proton of CH.sub.2), 2.14-2.03 (m, 1H, one proton of CH.sub.2), 2.03-1.84 (m, 2H, one proton of CH.sub.22), 1.83-1.67 (m, 1H, one proton of CH.sub.2), 1.34 (s, 12H, CH.sub.34); .sup.13C NMR (150 MHz, CDCl.sub.3): =171.0, 138.6, 135.1, 132.0, 128.0, 125.9, 83.8, 80.2, 29.6, 28.4, 24.824, 24.816, 18.3; IR (neat): =2977, 1731, 1607, 1357, 1233, 1142, 1087, 1033 cm.sup.1; MS (FI) m/z (%): 328 (M.sup.+(.sup.11B); HRMS Calcd. for C.sub.19H.sub.25O.sub.4.sup.10B (M.sup.+): 327.1877, found 327.1879.

Example 44

##STR00081##

[0101] Au(SIPr)Cl (31.3 mg, 0.05 mmol), AgOTf (12.8 mg, 0.05 mmol) and dioxane (1.25 mL) were added in sequence to a reaction flask. After stirring at room temperature for 15 minutes, 4 km (342.0 mg, 1.0 mmol) and water (36.0 mg, 2.0 mmol) were added in sequence. After stirring at room temperature for 24 hours, the reaction solution was filtered through a short silica gel column, and the filter cake was washed with diethyl ether (30 mL), concentrated, and purified by flash column chromatography (eluent:petroleum ether/ethyl acetate=4/1) to afford a product (E)-7 (252.9 mg, 70% yield): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): =7.76 (d, J=7.6 Hz, 2H, ArH), 7.37 (d, J=8.0 Hz, 2H, ArH), 6.59 (d, J=16.0 Hz, 1H, CH), 6.28 (dd, J.sub.1=15.6 Hz, J.sub.2=6.4 Hz, 1H, CH), 4.36-4.24 (m, 1H, CH), 3.67 (s, 3H, OCH.sub.3), 2.38 (t, J=7.2 Hz, 2H, CH.sub.2), 1.88-1.59 (m, 5H, CH.sub.22 and OH), 1.34 (s, 12H, CH.sub.34); .sup.13C NMR (100 MHz, CDCl.sub.3): =174.0, 139.3, 135.0, 133.1, 130.3, 125.7, 83.7, 72.4, 51.5, 36.5, 33.7, 24.8, 20.8; IR (neat): =3466, 2978, 1732, 1608, 1357, 1142, 1087 cm.sup.1; MS (FI) m/z (%): 360 (M.sup.+(.sup.11B); HRMS Calcd. for C.sub.20H.sub.29O.sub.5.sup.10B (M.sup.+): 359.2139, found 359.2148.

Example 45

##STR00082##

[0102] Under an argon atmosphere, Pd(PPh.sub.3).sub.2Cl.sub.2 (7.0 mg. 0.01 mmol), potassium carbonate (55.6 mg, 0.4 mmol), 4 km (68.4 mg, 0.2 mmol), 3-Bromoquinoline (62.7 mg, 0.3 mmol), freshly distilled dioxane (1 mL) and water (0.5 mL) were added in sequence to a dry reaction flask. The reaction flask was put into an oil bath at 80 C. for 5 hours. The reaction solution was filtered with a short silica gel column, and the filter cake was washed with ether, concentrated, and purified by flash column chromatography (eluent:petroleum ether/ethyl acetate=3/1) to afford a product 8 (54.3 mg, 95% purity, 75% yield): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): =9.19 (d, J=2.4 Hz, 1H, ArH), 8.30 (d, J=2.0 Hz, 1H, ArH), 8.13 (d, J=8.4 Hz, 1H, ArH), 7.88 (d, J=8.0 Hz, 1H, ArH), 7.76-7.69 (m, 1H, ArH), 7.67 (d, J=8.4 Hz, 2H, ArH), 7.62-7.54 (m, 1H, ArH), 7.44 (d, J=8.4 Hz, 2H, ArH), 6.23 (dt, J.sub.1=6.1 Hz, J.sub.2=3.0 Hz, 1H, CH), 5.63 (q, J=6.5 Hz, 1H, CH), 3.68 (s, 3H, OCH.sub.3), 2.42 (t, J=7.4 Hz, 2H, CH.sub.2), 2.29-2.13 (m, 2H, CH.sub.2), 1.92-1.80 (m, 2H, CH.sub.2); .sup.13C NMR (100 MHz, CDCl.sub.3): =205.6, 173.8, 149.7, 147.2, 136.1, 134.8, 133.4, 132.7, 129.25, 129.16, 128.0, 127.9, 127.5, 127.3, 126.9, 94.6, 94.3, 51.5, 33.3, 28.0, 24.2; IR (neat): =2948, 1946, 1731, 1515, 1492, 1435, 1340, 1195, 1149 cm.sup.1; MS (ESI) m z (%): 344 (M+H.sup.+); HRMS Calcd. for C.sub.23H.sub.22NO.sub.2 (M+H.sup.+): 344.1645, found 344.1644.

Example 46

##STR00083##

[0103] 4 km (68.8 mg, 0.2 mmol), ammonium acetate (92.6 mg, 1.2 mmol), sodium periodate (257.1 mg, 1.2 mmol), acetone (2.4 mL) and distilled water (1.2 mL) were added in sequence to a reaction flask. After reacting at room temperature for 12 hours, the reaction solution was filtered with a short silica gel column, and the filter cake was washed with acetone (15 mL), concentrated, extracted with diethyl ether (4 mL3), and the organic phases were combined, dried over anhydrous sodium sulfate, filtered, concentrated, purified by flash column chromatography (eluent dichloromethane/methanol=80/1) to afford the corresponding boronic acid (47.9 mg).

[0104] Pd(PPh.sub.3).sub.2Cl.sub.2 (3.9 mg, 5.5610.sup.3 mmol), potassium carbonate (76.5 mg, 0.554 mmol) and the above prepared boronic acid (47.9 mg, 0.184 mmol) were added in sequence to a dry reaction flask. After the reaction tube was plugged with a rubber stopper, inserted with a carbon monoxide balloon, connected to a vacuum pump, and replaced with the carbon monoxide three times under a carbon monoxide atmosphere. Then 1.1 mL of iodobenzene (41.4 mg, 0.203 mmol) in anisole solution was added. The reaction flask was placed in an oil bath at 80 C. and stirred for 6 hours. The reaction solution was filtered through a short silica gel column, and the filter cake was washed with diethyl ether (15 mL), concentrated, and purified by flash column chromatography (eluent:petroleum ether/ethyl acetate=20/1) to afford a product 9 (37.3 mg, 58% yield): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): =7.78 (t, J=8.4 Hz, 4H, ArH), 7.62-7.53 (m, 1H, ArH), 7.48 (t, J=7.6 Hz, 2H, ArH), 7.38 (d, J=8.4 Hz, 2H, ArH), 6.22 (dt, J.sub.1=6.3 Hz, J.sub.2=3.1 Hz, 1H, CH), 5.64 (q, J=6.5 Hz, 1H, CH), 3.67 (s, 3H, OCH.sub.3), 2.41 (t, J.sub.1=7.4 Hz, 2H, CH.sub.2), 2.21 (qd, J.sub.1=7.1 Hz, J.sub.2=2.9 Hz, 2H, CH.sub.2), 1.91-1.78 (m, 2H, CH.sub.2); .sup.13C NMR (100 MHz, CDCl.sub.3): =206.5, 196.2, 173.8, 139.5, 137.8, 135.7, 132.2, 130.6, 129.9, 128.2, 126.3, 94.7, 94.6, 51.6, 33.3, 27.8, 24.1; IR (neat): =2949, 1945, 1732, 1652, 1599, 1435, 1306, 1275, 1174, 1148 cm.sup.1; MS (ESI) m/z (%): 321 (M+H.sup.+); HRMS Calcd. for C.sub.21H.sub.21O.sub.3 (M+H.sup.+): 321.1485, found 321.1484.

Example 47

##STR00084##

[0105] The operation is the same as Example 1. 5 molecular sieves (250.4 mg), Au3d (43.5 mg, 0.05 mmol), aldehyde 1y (382.3 mg, 1.8 mmol), 1-methyl-1,2,3,4-tetrahydroisoquinoline 3f (176.5 mg, 1.2 mmol) and terminal alkyne 2p (202.1 mg, 1.0 mmol) were reacted in 2,2,2-trifluoroethanol (1 mL) to afford an allene product 4yp (255.2 mg, 64% yield) (purified by flash column chromatography (eluent:petroleum ether/ethyl acetate=40/1)): white solid; m.p. 71.0-72.2 C. (recrystallized from ether); .sup.1H NMR (400 MHz, CDCl.sub.3): =7.89 (d, J=8.8 Hz, 2H, ArH), 7.45-7.34 (m, 4H, ArH), 7.34-7.27 (m, 1H, ArH), 7.20 (d, J=8.4 Hz, 2H, ArH), 6.89 (d, J=8.8 Hz, 4H, ArH), 6.15-6.06 (m, 1H, CH), 5.56 (q, J=6.5 Hz, 1H, CH), 5.03 (s, 2H, CH.sub.2), 3.85 (s, 3H, OCH.sub.3), 2.97 (t, J=7.4 Hz, 2H, CH.sub.2), 2.28-2.16 (m, 2H, CH.sub.2), 1.92 (quintet, J=7.1 Hz, 2H, CH.sub.2); .sup.13C NMR (100 MHz, CDCl.sub.3): =204.6, 198.5, 163.2, 157.7, 136.8, 130.2, 130.0, 128.4, 127.8, 127.6, 127.31, 127.28, 115.0, 113.5, 94.30, 94.25, 69.9, 55.3, 37.3, 28.4, 23.5; IR (neat): =2897, 2840, 1943, 1670, 1602, 1577, 1509, 1231, 1167 cm.sup.1; MS (70 eV, EI) m/z (%): 398 (M.sup.+, 3.73), 91 (100).

[0106] Those skilled in the art will understand that within the protection scope of the present invention, it is feasible to modify, add and replace the above-mentioned embodiments, and none of them exceeds the protection scope of the present invention.