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Umpolung of Methylenephosphonium Ions in Their Manganese Half‐Sandwich Complexes and Application to the Synthesis of Chiral Phosphorus‐Containing Ligand Scaffolds
Author(s) -
Valyaev Dmitry A.,
Filippov Oleg A.,
Lugan Noël,
Lavigne Guy,
Ustynyuk Nikolai A.
Publication year - 2015
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201501256
Subject(s) - phosphine , umpolung , chemistry , manganese , ligand (biochemistry) , nucleophile , medicinal chemistry , phosphorus , yield (engineering) , stereochemistry , organic chemistry , catalysis , materials science , receptor , biochemistry , metallurgy
Abstract Half‐sandwich manganese methylenephosphonium complexes [Cp(CO) 2 Mn(η 2 ‐R 2 PC(H)Ph)]BF 4 were obtained in high yield through a straightforward reaction sequence involving a classical Fischer‐type manganese complex and a secondary phosphine as key starting materials. The addition of various nucleophiles (Nu) to these species took place regioselectively at the double‐bonded carbon center of the coordinated methylenephosphonium ligand R 2 P + C(H)Ph to produce the corresponding chiral phosphine complexes [Cp(CO) 2 Mn(κ 1 ‐R 2 PC(H)(Ph)Nu)], from which the phosphines were ultimately recovered as free entities upon simple irradiation with visible light. The synthetic potential of this umpolung approach is illustrated herein by the preparation of novel chiral pincer‐type phosphine–NHC–phosphine ligand architectures.