[3,3] Sigmatropic Rearrangement Versus [2+2] Cycloaddition: A DFT Investigation of Formal S N 2′ Substitution of Imido Metal Complexes with Allylic Electrophiles | Zendy

Cheng Caihong | Zendy; Chen Danfeng | Zendy; Wang Zhihong | Zendy

Premium

[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).

This content is not available in your region!

Continue researching here.

Having issues? You can contact us here

Accelerating Research