Facile Alder-Ene Reactions of Silylallenes Involving an Allenic C(sp(2) )-H Bond.
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.
Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago, IL, 60607 (USA).
Venkata R
VR
Sabbasani
Department of Chemistry, School of Science, Tianjin University, Tianjin 300072 (P.R. China).
Genping
G
Huang
College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, Zhejiang Province 325035 (P.R. China).
Yuanzhi
Y
Xia
Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago, IL, 60607 (USA). dsunglee@uic.edu.
Daesung
D
Lee
alder-ene reaction; allenic CH bonds; azodicarboxylates; bond dissociation energy; silylallenes