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Pentacoordinated Carboxylate π‐Allyl Nickel Complexes as Key Intermediates for the Ni‐Catalyzed Direct Amination of Allylic Alcohols
Author(s) -
Kita Yusuke,
Sakaguchi Hironobu,
Hoshimoto Yoichi,
Nakauchi Daisuke,
Nakahara Yasuhito,
Carpentier JeanFrançois,
Ogoshi Sensuke,
Mashima Kazushi
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201502329
Subject(s) - allylic rearrangement , chemistry , amination , carboxylate , cationic polymerization , catalysis , medicinal chemistry , regioselectivity , nickel , ferrocene , organic chemistry , electrochemistry , electrode
Direct amination of allylic alcohols with primary and secondary amines catalyzed by a system made of [Ni(1,5‐cyclooctadiene) 2 ] and 1,1′‐bis(diphenylphosphino)ferrocene was effectively enhanced by adding n Bu 4 NOAc and molecular sieves, affording the corresponding allyl amines in high yield with high monoallylation selectivity for primary amines and high regioselectivity for monosubstituted allylic alcohols. Such remarkable additive effects of n Bu 4 NOAc were elucidated by isolating and characterizing some nickel complexes, manifesting the key role of a charge neutral pentacoordinated η 3 ‐allyl acetate complex in the present system, in contrast to usual cationic tetracoordinated complexes earlier reported in allylic substitution reactions.