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Origin of Chemoselectivity of TMP Zincate Bases and Differences between TMP Zincate and Alkyl Lithium Reagents: A DFT Study on Model Systems
Author(s) -
Uchiyama Masanobu,
Matsumoto Yotaro,
Usui Shinya,
Hashimoto Yuichi,
Morokuma Keiji
Publication year - 2007
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.200602664
Subject(s) - chemoselectivity , zincate , chemistry , lithium (medication) , benzonitrile , alkyl , reagent , metalation , medicinal chemistry , combinatorial chemistry , organic chemistry , psychology , catalysis , zinc , psychiatry
Transition‐state structures of the type illustrated were found to be crucial in determining whether directed ortho ‐metalation (DoM) or 1,2‐addition occurs in the reaction of benzonitrile or methyl benzoate with Me 2 Zn(TMP)Li or (MeLi) 2 . The origin of the high chemoselectivity of the reaction was investigated. TMP=2,2,6,6‐tetramethylpiperidide.