135219-22-6Relevant articles and documents
Mechanistic Investigation of Well-Defined Cobalt Catalyzed Formal E-Selective Hydrophosphination of Alkynes
Rajpurohit, Jitendrasingh,Kumar, Pardeep,Shukla, Pragya,Shanmugam, Muralidharan,Shanmugam, Maheswaran
, p. 2297 - 2304 (2018)
A formal E-selective hydrophosphination of terminal and internal alkynes catalyzed by a well-defined [Co(PMe3)4] (A) complex is achieved under mild conditions in good-to-excellent yield. The reaction does not require any additives and/or external base for an efficient hydrophosphination reaction. The reaction provided excellent scope and good functional tolerance. Detailed spectroscopic analysis (NMR, EPR, and UV-vis) revealed that the low valent cobalt(0) complex undergoes oxidative addition with diphenylphosphine, followed by hydrometalation with alkyne, and subsequent reductive elimination led to the expected product. The detailed spectroscopic analyses along with the isotopic labeled experiments facilitate to intercept the active intermediates that are involved in the catalytic cycle, which are detailed. It was revealed that the suprafacial (vide infra) delivery of H and phosphorus to π-alkynes in a syn-fashion led to formal E-vinyl phosphine.
Preparation of vinylphosphines by means of free radical addition of diphenylphosphine to alkynes and allenes
Mitchell, Terence N.,Heesche, Kerstin
, p. 163 - 170 (2007/10/02)
Diphenylphosphine adds readily to alkynes and allenes under free radical conditions.Alkynes normally give E-vinylphosphines as the primary (kinetic) product, but Z-vinylphosphines are the main products isolated.Allenes generally give complex product mixtures in which the predominant components are vinyl phosphines formed via addition of the Ph2P. radical to the central carbon atom of the allene fragment.
