Cobalt-catalyzed highly regio- and stereoselective intermolecular reductive coupling of alkynes with conjugated alkenes

Chun-Chih Wang; Pao-Shun Lin; Chien-Hong Cheng

doi:10.1021/ja026543l

Cobalt-catalyzed highly regio- and stereoselective intermolecular reductive coupling of alkynes with conjugated alkenes

J Am Chem Soc. 2002 Aug 21;124(33):9696-7. doi: 10.1021/ja026543l.

Authors

Chun-Chih Wang¹, Pao-Shun Lin, Chien-Hong Cheng

Affiliation

¹ Department of Chemistry, Tsing Hua University, Hsinchu, Taiwan 300, China.

PMID: 12175214
DOI: 10.1021/ja026543l

Abstract

In the presence of Co(PPh3)2I2, PPh3, water, and zinc powder, the reaction of alkynes (R1CCR2: R1 = Ph, R2 = Me (1a); R1 = Ph, R2 = Ph (1b); R1 = Et, R2 = Et (1c); R1 = Ph, R2 = (CH2)3OH (1d); R1 = CO2Et, R2 = Ph (1e); R1 = CO2Me, R2 = (CH2)4CH3 (1f); R1 = CO2Et, R2 = SiMe3 (1g)) with alkenes having an electron-withdrawing substituent (CH2=CHR: R = CO2Bu (2a), CN (2b), SO2Ph (2c) and CO2Me (2d)) proceeded smoothly in acetonitrile to give the corresponding reductive coupling products (R1HC=CR2CH2CH2R, 3a-j) in fair to excellent yields. This reductive coupling is highly regio- and stereoselective; only one isomer was observed for each reaction. The results of an isotope-labeling experiment using D2O (99%) to replace normal water for the reductive coupling of vinyl phenyl sulfone 2c with alkyne 1a revealed that the product is E-Ph(D)C=CMeCH2CH(D)SO2Ph deuterated at the olefinic proton and one of the protons of the alpha-methylene group in 84 and 96%, respectively. Possible mechanisms for this highly regio- and stereoselective ene-yne catalytic reaction are proposed.