Platinum-catalysed allylic alkylation: reactivity, enantioselectivity, and regioselectivity

Chemistry : a European Journal
A J BlackerJ M Williams

Abstract

The use of platinum complexes as catalysts for allylic substitution has been studied. A variety of different complexes catalyse the reaction, and several substrates have been tested. In the alkylation of mono(alkyl)-substituted allylic acetates, regioselectivity is highly dependent on ligand choice. By using tricyclohexylphosphine as the ligand, almost complete formation of branched products is observed. The development of a highly enantioselective (ca. 80-90% ee) reaction that makes use of chiral diphenylphosphinooxazoline ligands (abbreviated as (S)-PN) is also described. The enantioselectivity is highly dependent on the ratio of ligand to platinum (when the ratio ligand/Pt is greater than 1:1, the ee drops off dramatically). This is in contrast to palladium and is interpreted in terms of differing coordination chemistry for the two metals ((S)-PN is hemilabile when complexed to platinum) and should be of significance to future systems that utilise heterobidentate ligands. The crystal structures of two isoelectronic platinum and palladium complexes [[(S)-PN]MCl2] are also described.

Citations

Apr 4, 2007·Dalton Transactions : an International Journal of Inorganic Chemistry·Dario DrommiCarlo Rosini
Oct 31, 2007·Angewandte Chemie·Zhan Lu, Shengming Ma
Nov 15, 2006·Dalton Transactions : an International Journal of Inorganic Chemistry·Carly E AndersonJudith A K Howard
Nov 2, 2007·The Journal of Organic Chemistry·Brandon L AshfeldStephen F Martin
Sep 25, 2003·Journal of the American Chemical Society·Thomas P Clark, Clark R Landis
May 26, 2018·Journal of the American Chemical Society·Sheng-Biao TangShu-Li You
Aug 5, 2003·The Journal of Organic Chemistry·Takatoshi KanayamaYoshiji Takemoto

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