|
|||||
|
|
Rhodium-catalyzed highly selective thioformylation of acetylenes with thiols and carbon monoxide |
|
| Authors: | Jun-ichi KawakamiMitsuhiro Takeba Ikuyo KamiyaNoboru Sonoda Akiya Ogawa |
| Affiliation: | a Chemical Development Laboratories, Takeda Chemical Industries, Ltd., 2-17-85 Jusohonmachi, Yodogawa-ku, Osaka 532-8686, Japan b Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565-0871, Japan c Department of Chemistry, Faculty of Science, Nara Women's University, Kitauoyanishi-machi, Nara 630-8506, Japan d Department of Applied Chemistry, Faculty of Engineering, Kansai University, Suita, Osaka 564-0073, Japan |
| Abstract: | Highly regioselective thioformylation of terminal acetylenes with thiols and carbon monoxide has been developed by the use of rhodium(I) complexes as the catalyst: formyl and thio groups are introduced into the terminal and inner positions of acetylenes, respectively. The thioformylation is performed in the presence of a catalytic amount of rhodium(I) complexes, such as RhH(CO)(PPh3)3, RhCl(PPh3)3, and RhCl(CO)(PPh3)2, under the pressure of CO (3 MPa) at 120°C in CH3CN to provide β-thio-α,β-unsaturated aldehydes in good yields. This thioformylation can be applied to a variety of terminal acetylenes and aromatic thiols. A mechanistic proposal includes the formation of the rhodium sulfide complex as the key species. |
| Keywords: | thioformylation rhodium thiols carbon monoxide acetylenes Wilkinson catalyst |
| 本文献已被 ScienceDirect 等数据库收录！ | |