title: Pentacoordinated carboxylate π-allyl nickel complexes as key intermediates for the Ni-catalyzed direct amination of allylic alcohols.
abstract: 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.
authors: Department of Chemistry, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531 (Japan).
authors: Yusuke
authors: Y
authors: Kita
authors: Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565-0871 (Japan).
authors: Hironobu
authors: H
authors: Sakaguchi
authors: Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565-0871 (Japan).
authors: Yoichi
authors: Y
authors: Hoshimoto
authors: Department of Chemistry, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531 (Japan).
authors: Daisuke
authors: D
authors: Nakauchi
authors: Department of Chemistry, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531 (Japan).
authors: Yasuhito
authors: Y
authors: Nakahara
authors: Institut des Sciences Chimiques de Rennes, Organometallics: Materials and Catalysis Dept. UMR 6226 CNRS-Université de Rennes 1, 35042 Rennes Cedex (France). jean-francois.carpentier@univ-rennes1.fr.
authors: Jean-François
authors: JF
authors: Carpentier
authors: Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565-0871 (Japan). ogoshi@chem.eng.osaka-u.ac.jp.
authors: Sensuke
authors: S
authors: Ogoshi
authors: Department of Chemistry, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531 (Japan). mashima@chem.es.osaka-u.ac.jp.
authors: Kazushi
authors: K
authors: Mashima
keywords: allylic compounds; amination; amines; nickel; reaction mechanisms