Convenient Methods for the Synthesis of a Library of Hemilabile Phosphines

Abstract

A series of novel functionalized phosphines of hemi­labile character, R₂P(CH₂)_nZ, have been prepared from diaryl­phosphines using several synthetic methodologies. The synthetic methods include the alkylation of lithium diarylphosphide or (di­arylphosphino)borane adducts with functionalized halogenoalkanes, X(CH₂)_nZ, and the photochemical hydrophosphination of suitable functionalized allyl or vinyl derivatives, H₂C=CHZ or H₂C=CHCH₂Z, using white light. A range of R₂PH (R = Bn, 4-MeOC₆H₄, 4-MeC₆H₄, 2-MeC₆H₄, Ph, 4-F₃CC₆H₄) has been used in order to tune the electronic density on the phosphorus donor atom. The coordination ability of the hemilabile fragment was modified by selection of the donor group (Z = OMe, OEt, OBu, NMe₂) or the length of the flexible carbon chain (n = 2, 3). Hemilabile fluorinated allylphosphines, R₂PCH₂CH=CH₂ (R = 4-FC₆H₄, C₆F₅), have been prepared from diarylchlorophosphines and allylmagnesium bromide.

Key words

hemilabile ligands - functionalized phosphines - hydrophosphination - allylphosphine

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