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

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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.

著者

Tomohiro Iwai Tomoya Harada Ryotaro Tanaka Masaya Sawamura

出版者

(社)日本化学会

雑誌

Chemistry Letters (ISSN:03667022)

巻号頁・発行日

pp.131161, (Released:2014-01-09)

被引用文献数

19

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Silica-supported tripod triarylphosphines that have a Ph3P-type core tripodally immobilized on silica surface enabled Pd-catalyzed borylation of chloroarenes with bis(pinacolato)diboron under mild conditions. The immobilization in tripod was crucial for the excellent performance of the Ph3P-based ligands.