ja5b09689_si_002.cif (27.19 kB)
Unique Steric Effect of Geminal Bis(silane) To Control the High Exo-selectivity in Intermolecular Diels–Alder Reaction
dataset
posted on 2016-01-22, 00:00 authored by Zengjin Liu, Xinglong Lin, Na Yang, Zhishan Su, Changwei Hu, Peihong Xiao, Yanyang He, Zhenlei SongThe unique steric effect of geminal
bis(silane) [(R3Si)2CH] allows an exo-selective intermolecular
Diels–Alder reaction of geminal bis(silyl) dienes with α,β-unsaturated
carbonyl compounds. The approach shows good generality to form ortho–trans cyclohexenes in good
yields with high exo-selectivity and high enantioselectivity
in some asymmetric cases. The excellent exo-stereocontrol
aptitude of (R3Si)2CH group is highlighted by
comparing with R3SiCH2 and R3Si groups,
which leads to endo-selectivity predominantly. The
conformational analysis of dienes suggests that (R3Si)2CH group effectively shields both sides of the diene moiety,
ensuring the desired exo-selectivity. Moreover, the
geminal bis(silane) can be further functionalized to transform the
resulting ortho–trans cycloadducts
into useful synthons, which makes the approach hold great potential
for organic synthesis.