Highly enantioselective catalytic methyl propiolate addition to both aromatic and aliphatic aldehydes

The excellent catalytic effect on methyl propiolate addition to a wide range of aromatic and aliphatic aldehydes promoted by inexpensive and commercially available BINOL-based ligand is reported. The catalyst systems showed high yields and excellent enantioselectivities for aromatic aldehydes, and excellent yields and high enantioselectivities for aliphatic aldehydes.

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Methyl 4-hydroxy-4-phenylbut-2-ynoateC11H10O3[α]D20 = −1.8 (c 0.950, CH2Cl2)Absolute configuration: not determined

Methyl 4-hydroxy-4-(o-tolyl)but-2-ynoateC12H12O3[α]D20 = +10.1 (c 1.0, CH2Cl2)Absolute configuration: not determined

Methyl 4-hydroxy-4-(m-tolyl)but-2-ynoateC12H12O3[α]D20 = −1.7 (c 0.35, CH2Cl2)Absolute configuration: not determined

Methyl 4-hydroxy-4-(p-tolyl)but-2-ynoateC12H12O3[α]D20 = −1.6 (c 0.985, CH2Cl2)Absolute configuration: not determined

Methyl 4-(4-(tert-butyl)phenyl)-4-hydroxybut-2-ynoateC15H18O3[α]D20 = −0.6 (c 1.13, CH2Cl2)Absolute configuration: not determined

Methyl 4-hydroxy-4-(2-methoxyphenyl)but-2-ynoateC12H12O4[α]D20 = −2.1 (c 1.22, CH2Cl2)Absolute configuration: not determined

Methyl 4-(2-fluorophenyl)-4-hydroxybut-2-ynoateC11H9FO3[α]D20 = +8.1 (c 1.105, CH2Cl2)Absolute configuration: not determined

Methyl 4-(2-chlorophenyl)-4-hydroxybut-2-ynoateC11H9ClO3[α]D20 = +35.5 (c 1.15, CH2Cl2)Absolute configuration: not determined

Methyl 4-(4-chlorophenyl)-4-hydroxybut-2-ynoateC11H9ClO3[α]D20 = −2.1 (c 0.235, CH2Cl2)Absolute configuration: not determined

Methyl 4-(naphthalen-1-yl)4-hydroxybut-2-ynoateC15H12O3[α]D20 = +5.2 (c 1.07, CH2Cl2)Absolute configuration: not determined

Methyl 4-(furan-2-yl)-4-hydroxybut-2-ynoateC9H8O4[α]D20 = −3.3 (c 1, CH2Cl2)Absolute configuration: not determined

Methyl 4-hydroxy-4-(thiophen-2-yl)but-2-ynoateC9H8O3S[α]D20 = −22.8 (c 1.01, CH2Cl2)Absolute configuration: not determined

Methyl 4-hydroxyhept-2-ynoateC8H12O3[α]D20 = −4.85 (c 1.05, CH2Cl2)Absolute configuration: not determined

Methyl 4-hydroxyoct-2-ynoateC9H14O3[α]D20 = −2.2 (c 1.05, CH2Cl2)Absolute configuration: not determined

Methyl 4-hydroxyundec-2-ynoateC12H20O3[α]D20 = +1.7 (c 1.06, CH2Cl2)Absolute configuration: not determined

Methyl 4-hydroxytridec-2-ynoateC14H24O3[α]D20 = +1.8 (c 1.08, CH2Cl2)Absolute configuration: not determined

Methyl 4-hydroxy-5-methylhex-2-ynoateC8H12O3[α]D20 = −0.4 (c 1.03, CH2Cl2)Absolute configuration: not determined

Methyl 5-ethyl-4-hydroxyhept-2-ynoateC10H16O3[α]D20 = +3.0 (c 1.09, CH2Cl2)Absolute configuration: not determined

Methyl 4-cyclopropyl-4-hydroxybut-2-ynoateC8H10O3[α]D20 = +35.3 (c 1.12, CH2Cl2)Absolute configuration: not determined

Methyl 4-hydroxy-5,5-dimethylhex-2-ynoateC9H14O3[α]D20 = −1.0 (c 1.07, CH2Cl2)Absolute configuration: not determined

Methyl 4-hydroxy-6-methylhept-2-ynoateC9H14O3[α]D20 = −8.5 (c 1.07, CH2Cl2)Absolute configuration: not determined

Methyl 4-hydroxy-5-phenylpent-2-ynoateC12H12O3[α]D20 = −0.4 (c 1.09, CH2Cl2)Absolute configuration: not determined

(E)-Methyl 4-hydroxy-6-phenylhex-5-en-2-ynoateC13H12O3[α]D20 = −1.6 (c 0.51, CH2Cl2)Absolute configuration: not determined

(E)-Methyl 4-hydroxydodec-5-en-2-ynoateC12H18O3[α]D20 = +40.2 (c 1.05, CH2Cl2)Absolute configuration: not determined