研究人员报道了一种前所未有的,手性双膦催化的2,2-二取代环己烷-1,3-二酮的不对称Staudinger/aza-Wittig反应,使其能够以优异的对映选择性以高产率获得广泛的顺式-3a-芳基氢吲哚。该项工作成功的关键在于手性双膦DuanPhos,首次应用于不对称Staudinger/aza-Wittig反应。
研究人员建立了一个有效的还原系统来解决,具有挑战性的PV═O/PIII与手性双膦催化剂相关的氧化还原循环。此外,研究人员还进行了全面的实验和计算研究,以阐明不对称反应的机理。利用新开发的化学方法,高效地完成了几种Crinine型石蒜科生物碱的对映选择性全合成,包括(+)-鲍威文殊兰碱、(+)-布蕃胺、(+)-条纹(小星蒜)碱以及(+)-crinane。
附:英文原文
Title: Chiral Bisphosphine-Catalyzed Asymmetric Staudinger/aza-Wittig Reaction: An Enantioselective Desymmetrizing Approach to Crinine-Type Amaryllidaceae Alkaloids
Author: Hongzhi Yang, Jingyang Zhang, Sen Zhang, Zhengwen Xue, Shengkun Hu, Yi Chen, Yefeng Tang
Issue&Volume: April 20, 2024
Abstract: An unprecedented chiral bisphosphine-catalyzed asymmetric Staudinger/aza-Wittig reaction of 2,2-disubstituted cyclohexane-1,3-diones is reported, enabling the facile access of a broad range of cis-3a-arylhydroindoles in high yields with excellent enantioselectivities. The key to the success of this work relies on the first application of chiral bisphosphine DuanPhos to the asymmetric Staudinger/aza-Wittig reaction. An effective reductive system has been established to address the challenging PV═O/PIII redox cycle associated with the chiral bisphosphine catalyst. In addition, comprehensive experimental and computational investigations were carried out to elucidate the mechanism of the asymmetric reaction. Leveraging the newly developed chemistry, the enantioselective total syntheses of several crinine-type Amaryllidaceae alkaloids, including (+)-powelline, (+)-buphanamine, (+)-vittatine, and (+)-crinane, have been accomplished with remarkable conciseness and efficiency.
DOI: 10.1021/jacs.4c02755
Source: https://pubs.acs.org/doi/abs/10.1021/jacs.4c02755
JACS:《美国化学会志》,创刊于1879年。隶属于美国化学会,最新IF:16.383
官方网址:https://pubs.acs.org/journal/jacsat
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