TY - JOUR
T1 - Origin of chemoselectivity of TMP zincate bases and differences between TMP zincate and alkyl lithium reagents
T2 - A DFT study on model systems
AU - Uchiyama, Masanobu
AU - Matsumoto, Yotaro
AU - Usui, Shinya
AU - Hashimoto, Yuichi
AU - Morokuma, Keiji
PY - 2007
Y1 - 2007
N2 - (Chemical Equation Presented) 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 Me2Zn(TMP)Li or (MeLi)2. The origin of the high chemoselectivity of the reaction was investigated. TMP = 2,2,6,6-tetramethylpiperidide.
AB - (Chemical Equation Presented) 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 Me2Zn(TMP)Li or (MeLi)2. The origin of the high chemoselectivity of the reaction was investigated. TMP = 2,2,6,6-tetramethylpiperidide.
KW - Chemoselectivity
KW - Density functional calculations
KW - Metalation
KW - Transition states
KW - Zincates
UR - http://www.scopus.com/inward/record.url?scp=33846661111&partnerID=8YFLogxK
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U2 - 10.1002/anie.200602664
DO - 10.1002/anie.200602664
M3 - Article
C2 - 17167804
AN - SCOPUS:33846661111
SN - 1433-7851
VL - 46
SP - 926
EP - 929
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 6
ER -