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Facile Alder‐Ene Reactions of Silylallenes Involving an Allenic C(sp 2 )H Bond
Author(s) -
Sabbasani Venkata R.,
Huang Genping,
Xia Yuanzhi,
Lee Daesung
Publication year - 2015
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.201503243
Subject(s) - ene reaction , allylic rearrangement , chemistry , reactivity (psychology) , silylation , medicinal chemistry , substituent , selectivity , double bond , alkyl , dissociation (chemistry) , stereochemistry , catalysis , organic chemistry , medicine , alternative medicine , pathology
Facile and selective Alder‐ene reactions of silylallenes involving the activation of an allenic C(sp 2 )H over an allylic C(sp 3 )H bond is described. In this ene reaction, the presence of a silyl substituent was found to be critical for the observed reactivity and selectivity since the corresponding alkyl‐substituted allenes show different reaction profiles. Computational studies show that the origin of this unusual reactivity is the lower bond dissociation energy of the α‐C(sp 2 )H bond in silylallenes compared to the corresponding nonsilylated allenes.