American Chemical Society
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Reactions of Tri-tert-Butylphosphatetrahedrane as a Spring-Loaded Phosphinidene Synthon Featuring Nickel-Catalyzed Transfer to Unactivated Alkenes

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Version 2 2022-04-19, 21:08
Version 1 2022-04-18, 21:45
journal contribution
posted on 2022-04-19, 21:08 authored by Martin-Louis Y. Riu, André K. Eckhardt, Christopher C. Cummins
Cage-opening reactions of the highly strained tri-tert-butylphosphatetrahedrane (1), shown here to function as a synthon of (tri-tert-butylcyclopropenyl)­phosphinidene, are described. Treatment of 1 with a base-stabilized silylene led to the corresponding phosphasilene, which was isolated in 72% yield as a red crystalline solid. Phosphinidene transfer was also observed when 1 (2 equiv) was combined with the Wittig reagent Ph3PCH2 to form a diphosphirane (50% isolated yield). The reaction is proposed to proceed through a generated phosphaalkene intermediate, which was characterized by NMR spectroscopy. In addition, we report on nickel-catalyzed phosphinidene transfer to styrene, ethylene, neohexene, and 1,3-cyclohexadiene; the corresponding phosphiranes were isolated in 51–64% yield. Computational studies suggest the intermediacy of a nickel phosphinidene species. Treatment of the ethylene-derived phosphirane product with triflic acid delivered elimination of [tBu3C3]­OTf and formation of a P–H bond, illustrating the ability of the tri-tert-butyl cyclopropenyl group to serve as a protecting group that is removable following phosphinidene transfer.