Unique Steric Effect of Geminal Bis(silane) To Control the High Exo-selectivity in Intermolecular Diels-Alder Reaction

Journal of the American Chemical Society
Zengjin LiuZhenlei Song

Abstract

The 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.

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Citations

Oct 13, 2016·Scientific Reports·Guo-Ming HoShang-Cheng Hung
Jan 17, 2017·Angewandte Chemie·Lihao LiaoXiaodan Zhao
Jun 28, 2018·Organic & Biomolecular Chemistry·Kennosuke Itoh, Mukund P Sibi
Aug 31, 2018·Chemistry : a European Journal·Peihong XiaoZhenlei Song
Dec 7, 2017·Angewandte Chemie·Yuebao ZhangZhenlei Song
Feb 28, 2019·Organic & Biomolecular Chemistry·Jorge Juan Cabrera-Trujillo, Israel Fernández
Jun 15, 2021·Chemical Science·William J LordingMichael N Paddon-Row
Dec 15, 2017·The Journal of Organic Chemistry·Peihong XiaoZhenlei Song
Aug 15, 2019·The Journal of Organic Chemistry·Sebastián Gallardo-FuentesMarcelo Vilches-Herrera
May 24, 2018·Organic Letters·Bing JiangTeck-Peng Loh
Sep 23, 2021·Organic Letters·Min HouShuanhu Gao
Oct 13, 2021·Organic Letters·Wanna SungnoiMichael Harmata

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