Citation: Xiaohui Fu, Yanping Zhang, Juan Liao, Zhen-Hua Wang, Yong You, Jian-Qiang Zhao, Mingqiang Zhou, Wei-Cheng Yuan. Palladium-catalyzed enantioselective decarboxylation of vinyl cyclic carbamates: Generation of amide-based aza-1,3-dipoles and application to asymmetric 1,3-dipolar cycloaddition[J]. Chinese Chemical Letters, ;2024, 35(12): 109688. doi: 10.1016/j.cclet.2024.109688 shu

Palladium-catalyzed enantioselective decarboxylation of vinyl cyclic carbamates: Generation of amide-based aza-1,3-dipoles and application to asymmetric 1,3-dipolar cycloaddition

Xiaohui Fu ^{a, b, c} ,
Yanping Zhang ^b ,
Juan Liao ^{a, b, c} ,
Zhen-Hua Wang ^b ,
Yong You ^b ,
Jian-Qiang Zhao ^b ,
Mingqiang Zhou ^{a, b, c} ,
Wei-Cheng Yuan ^{a, b, c, *,}

a.
National Engineering Research Center of Chiral Drugs, Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041, China
b.
Innovation Research Center of Chiral Drugs, Institute for Advanced Study, Chengdu University, Chengdu 610106, China
c.
University of Chinese Academy of Sciences, Beijing 100049, China

yuanwc@cioc.ac.cn

Received Date: 20 August 2023
Revised Date: 20 February 2024
Accepted Date: 27 February 2024
Available Online: 1 March 2024

Figures(7)

The catalytic asymmetric dipolar cycloaddition reaction is efficient for the construction of various chiral valuable carbo- and heterocycles. Thus, the design and exploration of new dipoles and the subsequent control of their reactivity for various stereoselective cycloadditions are significant aspects of modern organic synthesis. Herein, we have developed a series of vinyl cyclic carbamates containing an oxazolidine-2,4–dione fragment and used them as reactive precursors for in situ generation of amide-based aza-π-allylpalladium 1,3-dipoles, which could be applied to asymmetric decarboxylative 1,3-dipolar cycloaddition with different types of dipolarophiles containing C=C, C=N, and C=O double bonds. This strategy provides an opportunity for the synthesis of previously unusual structures, such as highly functionalized optically pure pyrrolidin-2-ones, imidazolidin-4-ones, and oxazolidin-4-ones. This protocol also has significant features including wide substrate scope, mild reaction conditions, simple operation, and good to excellent results (70 examples, up to 99% yield, >20:1 dr and 99% ee). This unique method significantly expands the reaction range of the amide-based aza-π-allylpalladium 1,3-dipoles compared to the precedents.
- Cycloaddition,
- Palladium,
- Enantioselectivity,
- Asymmetric catalysis,
- Decarboxylation
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