Xie Yu-Yang, Chen Zhi-Min, Luo Hui-Yun, Shao Hui, Tu Yong-Qiang, Bao Xiaoguang, Cao Ren-Fei, Zhang Shu-Yu, Tian Jin-Miao
School of Chemistry and Chemical Engineering and Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240, P. R. China.
State Key Laboratory of Applied Organic Chemistry and College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, 730000, P. R. China.
Angew Chem Int Ed Engl. 2019 Sep 2;58(36):12491-12496. doi: 10.1002/anie.201907115. Epub 2019 Aug 7.
An enantioselective sulfenylation/semipinacol rearrangement of 1,1-disubstituted and trisubstituted allylic alcohols was accomplished with a chiral Lewis base and a chiral Brønsted acid as cocatalysts, generating various β-arylthio ketones bearing an all-carbon quaternary center in moderate to excellent yields and excellent enantioselectivities. These chiral arylthio ketone products are common intermediates with many applications, for example, in the design of new chiral catalysts/ligands and the total synthesis of natural products. Computational studies (DFT calculations) were carried out to explain the enantioselectivity and the role of the chiral Brønsted acid. Additionally, the synthetic utility of this method was exemplified by an enantioselective total synthesis of (-)-herbertene and a one-pot synthesis of a chiral sulfoxide and sulfone.
在手性路易斯碱和手性布朗斯特酸作为共催化剂的作用下，实现了1,1 - 二取代和三取代烯丙醇的对映选择性亚磺酰化/半频哪醇重排反应，以中等至优异的产率和出色的对映选择性生成了各种带有全碳季碳中心的β - 芳硫基酮。这些手性芳硫基酮产物是具有许多应用的常见中间体，例如，用于设计新型手性催化剂/配体以及天然产物的全合成。进行了计算研究（密度泛函理论计算）以解释对映选择性和手性布朗斯特酸的作用。此外，该方法的合成实用性通过（-）- 海柏萜烯的对映选择性全合成以及手性亚砜和砜的一锅法合成得以例证。
