%0 Journal Article %T Pentacoordinated Carboxylate π-Allyl Nickel Complexes as Key Intermediates for the Ni-Catalyzed Direct Amination of Allylic Alcohols %+ Osaka University [Osaka] %+ Institut des Sciences Chimiques de Rennes (ISCR) %A Kita, Yusuke %A Nakauchi, Daisuke %A Nakahara, Yasuhito %A Mashima, Kazushi %A Sakaguchi, Hironobu %A Hoshimoto, Yoichi %A Ogoshi, Sensuke %A Carpentier, Jean-François %Z Ministry of Education, Culture, Sports, Science and Technology %Z Japan Science and Technology Agency %Z 23105546, Scientific Research on Innovative Area “Molecular Activation Directed toward Straightforward Synthesis” %Z Frontier Research Base for Global Young Researchers, Osaka University %< avec comité de lecture %J Chemistry %I Wiley %V 21 %N 41 %P 14571-14578 %8 2015-10-05 %D 2015 %R 10.1002/chem.201502329 %M 26307334 %K allylic compounds %K amination %K amines %K nickel %K reaction mechanisms %Z Chemical SciencesJournal articles %X 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. %G English %L hal-01191803 %U https://univ-rennes.hal.science/hal-01191803 %~ UNIV-RENNES1 %~ CNRS %~ INSA-RENNES %~ ENSC-RENNES %~ ISCR %~ SCR_OMC2012 %~ ISCR-OMC %~ STATS-UR1 %~ UR1-SPM %~ INC-CNRS %~ UR1-UFR-SPM %~ UR1-HAL %~ UR1-SDLM %~ UR1-SDLMJONCH %~ TEST-UNIV-RENNES %~ TEST-UR-CSS %~ UNIV-RENNES %~ INSA-GROUPE %~ UR1-MMS %~ TEST2-HALCNRS