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Transition-Metal Catalysis with Hollow-Shaped Triethynylphosphine Ligands

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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)
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

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