Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
The Chemical Society of Japan Award for Creative Work for 2011
Transition-Metal Catalysis with Hollow-Shaped Triethynylphosphine Ligands
Tomohiro IwaiMasaya Sawamura
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2014 Volume 87 Issue 11 Pages 1147-1160

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Abstract

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.

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 and the gold(I)-catalyzed alkyne cyclization constructing six- to eight-membered ring compounds. Fullsize Image
 
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© 2014 The Chemical Society of Japan
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