|
Hokkaido University Collection of Scholarly and Academic Papers >
Graduate School of Science / Faculty of Science >
Peer-reviewed Journal Articles, etc >
Transition-Metal Catalysis with Hollow-Shaped Triethynylphosphine Ligands
| Title: | Transition-Metal Catalysis with Hollow-Shaped Triethynylphosphine Ligands |
| Authors: | Iwai, Tomohiro Browse this author →KAKEN DB | | Sawamura, Masaya Browse this author →KAKEN DB |
| Issue Date: | 15-Nov-2014 |
| Publisher: | Chemical Society of Japan |
| Journal Title: | Bulletin of the Chemical Society of Japan |
| Volume: | 87 |
| Issue: | 11 |
| Start Page: | 1147 |
| End Page: | 1160 |
| Publisher DOI: | 10.1246/bcsj.20140186 |
| Abstract: | Triethynylphosphines with bulky end caps such as triarylsilyl and triarylmethyl groups at allcyne termini have a novel molecular shape presenting a large, deep metal-binding cavity. The hollow-shaped triethynylphosphines functioned as effective ligands in the rhodium-catalyzed hydrosilylation of ketones with triorganosilanes due to the preferential formation of a mono-P-ligated rhodium species. Furthermore, the phosphines displayed remarkable rate enhancement in the gold(I)-catalyzed alkyne cyclization constructing six- to eight-membered ring compounds. It is proposed that the cavity in the ligand forces a nucleophilic center of the acetylenic compounds close to the gold-bound alkyne, making ring-closing anti attack feasible. |
| Type: | article (author version) |
| URI: | http://hdl.handle.net/2115/57758 |
| Appears in Collections: | 理学院・理学研究院 (Graduate School of Science / Faculty of Science) > 雑誌発表論文等 (Peer-reviewed Journal Articles, etc)
|
Submitter: 澤村 正也
|
