Shim Su Yong, Choi Yuna, Ryu Do Hyun
Department of Chemistry , Sungkyunkwan University , Suwon 16419 , Korea.
School of Chemistry and Chemical Engineering , University of Jinan , Jinan 250022 , China.
J Am Chem Soc. 2018 Sep 12;140(36):11184-11188. doi: 10.1021/jacs.8b06835. Epub 2018 Aug 14.
Chiral Lewis acid catalyzed asymmetric formation of cyclobutanones from α-silyloxyacroleins and α-alkyl or α-aryl diazoesters has been developed. In the presence of a chiral oxazaborolidinium ion catalyst, various α-silyloxycyclobutanones possessing a chiral β-quaternary center were synthesized in high yield (up to 91%) with excellent enantio- and diastereoselectivity (up to 98% ee and up to >20:1 dr) through tandem cyclopropanation/semipinacol rearrangement. The synthetic potential of this method was illustrated by conversion of the product to various cyclic compounds such as γ-lactone, cyclobutanol, and cyclopentanone.
已经开发出手性路易斯酸催化的α-硅氧基丙烯醛与α-烷基或α-芳基重氮酯不对称形成环丁酮的反应。在一种手性恶唑硼烷鎓离子催化剂存在下，通过串联环丙烷化/半频哪醇重排，以高产率（高达91%）合成了各种具有手性β-季碳中心的α-硅氧基环丁酮，对映选择性和非对映选择性优异（高达98% ee和高达>20:1 dr）。该方法的合成潜力通过将产物转化为各种环状化合物（如γ-内酯、环丁醇和环戊酮）得以体现。
