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(NHC)NiH‐Catalyzed Intermolecular Regio‐ and Diastereoselective Cross‐Hydroalkenylation of Endocyclic Dienes with α‐Olefins
Author(s) -
Lian Xiaoyan,
Chen Weihao,
Dang Liang,
Li Yuchen,
Ho ChunYu
Publication year - 2017
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201703706
Subject(s) - cationic polymerization , chemistry , catalysis , selectivity , diene , olefin fiber , heteroatom , intermolecular force , medicinal chemistry , chirality (physics) , ligand (biochemistry) , stereochemistry , enantioselective synthesis , polymer chemistry , organic chemistry , molecule , ring (chemistry) , biochemistry , natural rubber , chiral symmetry breaking , physics , receptor , quantum mechanics , nambu–jona lasinio model , quark
Highly selective cross‐hydroalkenylations of endocyclic 1,3‐dienes at the least substituted site with α‐olefins were achieved with a set of neutral (NHC)Ni II H(OTf) catalysts and cationic Ni II catalysts with a novel NHC ligand. Under heteroatom assistance, skipped dienes were obtained in good yields, often from equal amounts of the two substrates and at a catalyst loading of 2–5 mol %. Rare 4,3‐product selectivity (i.e., with the H atom at C4 and the alkenyl group at C3 of the diene) was observed, which is different from the selectivity of known dimerizations of α‐olefins with both acyclic Co and Fe systems. The influence of the various substituents on the NHC, 1,3‐diene, and α‐olefin on the chemo‐, regio‐, and diastereoselectivity was studied. High levels of chirality transfer were observed with chiral cyclohexadiene derivatives.