Pentacoordinated Carboxylate π-Allyl Nickel Complexes as Key Intermediates for the Ni-Catalyzed Direct Amination of Allylic Alcohols - Université de Rennes Accéder directement au contenu
Article Dans Une Revue Chemistry Année : 2015

Pentacoordinated Carboxylate π-Allyl Nickel Complexes as Key Intermediates for the Ni-Catalyzed Direct Amination of Allylic Alcohols

Yasuhito Nakahara
  • Fonction : Auteur
Kazushi Mashima
  • Fonction : Auteur
Hironobu Sakaguchi
  • Fonction : Auteur
Yoichi Hoshimoto
  • Fonction : Auteur
Sensuke Ogoshi
  • Fonction : Auteur

Résumé

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 nBu4 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 nBu4 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.

Domaines

Chimie

Dates et versions

hal-01191803 , version 1 (02-09-2015)

Identifiants

Citer

Yusuke Kita, Daisuke Nakauchi, Yasuhito Nakahara, Kazushi Mashima, Hironobu Sakaguchi, et al.. Pentacoordinated Carboxylate π-Allyl Nickel Complexes as Key Intermediates for the Ni-Catalyzed Direct Amination of Allylic Alcohols. Chemistry , 2015, 21 (41), pp.14571-14578. ⟨10.1002/chem.201502329⟩. ⟨hal-01191803⟩
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