- 著者
-
Tomohiro Iwai
Masaya Sawamura
- 出版者
- (社)日本化学会
- 雑誌
- Bulletin of the Chemical Society of Japan (ISSN:00092673)
- 巻号頁・発行日
- vol.87, no.11, pp.1147-1160, 2014-11-15 (Released:2014-11-15)
- 参考文献数
- 107
- 被引用文献数
-
12
Triethynylphosphines with bulky end caps such as triarylsilyl and triarylmethyl groups at alkyne 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.