Modular Chiral-Aldehyde/Palladium Catalysis Enables Atom-Economical α-Allylation of N-Unprotected Amino Acid Esters with 1,3-Dienes and Allenes,ACS Catalysis

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Modular Chiral-Aldehyde/Palladium Catalysis Enables Atom-Economical α-Allylation of N-Unprotected Amino Acid Esters with 1,3-Dienes and Allenes
ACS Catalysis ( IF 11.3 ) Pub Date : 2023-04-18 , DOI: 10.1021/acscatal.3c00790
Jian-Hua Liu ₁ , Qing Zhou ₁ , Yao Lin ₁ , Zhu-Lian Wu ₁ , Tian Cai ₁ , Wei Wen ₁ , Yan-Min Huang ₂ , Qi-Xiang Guo ₁

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Herein, we report a chiral-aldehyde/palladium-catalyzed atom-economic asymmetric α-allylation of N-unprotected amino acid esters with unsaturated hydrocarbons. Chiral-aldehyde catalysis provides active nucleophilic intermediates from amino acid esters, while palladium catalysis provides the active electrophilic π-allyl metal species via hydrometallation of the unsaturated hydrocarbons. Accordingly, asymmetric α-allylation of N-unprotected amino acid esters with both 1,3-dienes and allenes can be achieved with high efficiency, allowing various α,α-disubstituted unnatural α-amino acid esters to be generated in good-to-excellent yields and stereoselectivities. No N-allylation byproducts are formed in these two reactions. Based on the results of mechanistic control experiments, two reaction models are proposed. Overall, this work demonstrates a completely atom-economical method for preparing structurally diverse chiral amino acids and provides guidance for developing further chiral-aldehyde catalytic systems.

中文翻译：

模块化手性醛/钯催化使 N-未保护氨基酸酯与 1,3-二烯和丙二烯的原子经济性 α-烯丙基化成为可能

在此，我们报告了 N-未保护氨基酸酯与不饱和烃的手性醛/钯催化原子经济不对称 α-烯丙基化反应。手性醛催化从氨基酸酯中提供活性亲核中间体，而钯催化通过不饱和烃的加氢金属化提供活性亲电子 π- 烯丙基金属物质。因此，N-未保护的氨基酸酯与 1,3-二烯和丙二烯的不对称 α-烯丙基化可以高效地实现，允许各种 α,α-二取代的非天然 α-氨基酸酯以良好的-优异的产率和立体选择性。在这两个反应中没有形成 N-烯丙基化副产物。基于机械控制实验的结果，提出了两种反应模型。全面的，

更新日期：2023-04-18

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