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[3,3] Sigmatropic Rearrangement Versus [2+2] Cycloaddition: A DFT Investigation of Formal S N 2′ Substitution of Imido Metal Complexes with Allylic Electrophiles
Author(s) -
Cheng Caihong,
Chen Danfeng,
Wang Zhihong
Publication year - 2013
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201203197
Subject(s) - sigmatropic reaction , substitution (logic) , allylic rearrangement , electrophile , computer science , cycloaddition , trimethylsilyl , chemistry , stereochemistry , world wide web , medicinal chemistry , programming language , organic chemistry , catalysis
Is common sense always best? A DFT investigation of two S N 2′ substitution reactions with different central metals (zirconium and titanium) and types of allylic sources revealed that in both cases, a [2+2]/retro‐[2+2] pathway is energetically favorable. This is in contrast with the usually accepted [3,3] sigmatropic rearrangement mechanism (see picture; TMS=trimethylsilyl).