Ir/Ru顺序催化立体发散性合成手性高烯丙醇：不对称级联烯丙基取代/Retro-Claisen/转移氢化★

doi:10.6023/A26070264

研究通讯

Ir/Ru顺序催化立体发散性合成手性高烯丙醇：不对称级联烯丙基取代/Retro-Claisen/转移氢化^★

刘祎^a, 丁虹雨^a, 江铭轩^a, 董秀琴^a,*, 王春江^a,b,*

^a湖北省化学基础学科研究中心, 化学与分子科学学院, 武汉大学, 武汉, 430072, 中国;
^b金属有机化学国家重点实验室, 中国科学院上海有机化学研究所, 上海, 230021, 中国

投稿日期:2026-07-24
作者简介:^★“不对称协同催化”专辑

Stereodivergent Synthesis of Chiral Homoallylic Carbinols via Ir/Ru Sequential Catalysis: Asymmetric Cascade Allylation/Retro-Claisen/Transfer Hydrogenation

Yi Liu^a, Hong-Yu Ding^a, Ming-Xuan Jiang^a, Xiu-Qin Dong^a,*, Chun-Jiang Wang^a,b,*

^aHubei Research Center of Fundamental Science-Chemistry, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, 430072, China;
^bState Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 230021, China

Received:2026-07-24
Contact: *E-mail: xiuqindong@whu.edu.cn (X.Q.D.); cjwang@whu.edu.cn (C.J.W.)
Supported by:
National Key R&D Program of China (2023YFA1506700), Fundamental Research Funds for the Central Universities (2042025kf0032), National Natural Science Foundation of China (22271226, 22371216, 22671266, and 22631010), and National Youth Talent Support Program.

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1. Supporting Information-A26070264.pdf(3955KB)

摘要/Abstract

我们运用铱/钌顺序催化体系实现手性高烯丙基醇的立体发散性构建。该一锅串联策略以易得的β-二酮和乙烯基碳酸亚乙烯酯（VEC）为起始原料,整合了铱催化的不对称烯丙基取代/逆-克莱森级联反应与后续的钌催化不对称转移氢化（ATH）,可便捷地获得一系列高度官能化的手性高烯丙基醇衍生物。这些产物含有非连续的1,3-叔碳/叔碳手性中心,产率中等至优良,立体选择性优异。通过调控四种不同构型的手性Ir/Ru催化剂组合,能够以优异的立体选择性高效获得目标产物的全部四种立体异构体,其中每个手性中心的构型均由两种不同的手性催化剂独立且精确控制。此外,克级规模合成实验以及一系列衍生化转化研究,说明该顺序催化方案的实用性和合成应用潜力。

关键词: 顺序催化, 手性高烯丙醇, 立体发散性合成, 串联反应, 不对称催化合成

Iridium/ruthenium sequential catalysis platform has been established for the stereodivergent construction of chiral homoallylic carbinols. This one-pot tandem protocol leverages readily accessible β-diketones and vinyl ethylene carbonate (VEC) as starting materials, integrating an Ir-catalyzed asymmetric allylation/retro-Claisen cascade process and a subsequent Ru-catalyzed asymmetric transfer hydrogenation (ATH). A diverse array of highly functionalized chiral homoallylic alcohol derivatives containing non-contiguous 1,3-tertiary/tertiary stereocenters could be easily obtained in moderate to good yields with excellent stereoselectivity. Fine manipulation of four distinct chiral Ir/Ru catalyst combinations allows facile access to all four stereoisomers of the target products with excellent stereoselectivity, wherein each stereogenic center is independently and precisely governed by the two distinct chiral catalysts. Furthermore, the practicality of this dual-catalytic protocol is demonstrated by gram-scale synthesis, and the versatile downstream derivatization of the obtained chiral homoallylic alcohols solidifies their utility as robust synthetic building blocks for the construction of complex chiral molecular scaffolds.

Key words: Sequential Catalysis, Chiral Homoallylic Carbinols, Stereodivergent Synthesis, Cascade Reaction, Asymmetric Catalytic Synthesis

引用此文

刘祎, 丁虹雨, 江铭轩, 董秀琴, 王春江. Ir/Ru顺序催化立体发散性合成手性高烯丙醇：不对称级联烯丙基取代/Retro-Claisen/转移氢化^★[J]. 化学学报, doi: 10.6023/A26070264.

Yi Liu, Hong-Yu Ding, Ming-Xuan Jiang, Xiu-Qin Dong, Chun-Jiang Wang. Stereodivergent Synthesis of Chiral Homoallylic Carbinols via Ir/Ru Sequential Catalysis: Asymmetric Cascade Allylation/Retro-Claisen/Transfer Hydrogenation[J]. Acta Chimica Sinica, doi: 10.6023/A26070264.

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