Pentacoordinated Carboxylate π-Allyl Nickel Complexes as Key Intermediates for the Ni-Catalyzed Direct Amination of Allylic Alcohols - Université de Rennes Access content directly
Journal Articles Chemistry Year : 2015

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

Yasuhito Nakahara
  • Function : Author
Kazushi Mashima
  • Function : Author
Hironobu Sakaguchi
  • Function : Author
Yoichi Hoshimoto
  • Function : Author
Sensuke Ogoshi
  • Function : Author

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.

Dates and versions

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

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Cite

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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