Synthesis of Chiral Nine-Membered N-Heterocycles through Silver(I)-Promoted Cycloaddition and Rearrangement from N-Vinyl-α,β-Unsaturated Nitrones with Chiral 3-Propioloyloxazolidin-2-Ones,Advanced Synthesis & Catalysis

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Synthesis of Chiral Nine-Membered N-Heterocycles through Silver(I)-Promoted Cycloaddition and Rearrangement from N-Vinyl-α,β-Unsaturated Nitrones with Chiral 3-Propioloyloxazolidin-2-Ones
Advanced Synthesis & Catalysis ( IF 4.4 ) Pub Date : 2021-11-26 , DOI: 10.1002/adsc.202101199
Xiao-Ting Qin ₁ , Ning Zou ₁ , Xiao-Ling Cheng ₁ , Cui Liang ₁ , Dong-Liang Mo ₁

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A variety of chiral nine-membered N-heterocycles were prepared in moderate to good yields with high diastereoselectivity through a silver(I)-catalyzed [3+2] cycloaddition and [3,3]-rearrangement of N-vinyl-α, β-unsaturated nitrones and chiral 3-propioloyloxazolidin-2-ones. Experimental studies showed that silver catalyst promoted the cycloaddition and rearrangement process, and the stereochemistry of the nine-membered N-heterocycles was controlled via [3,3]-rearrangement by chiral oxazolidinone-auxiliary through a boat-like transition state. Moreover, the obtained nine-membered N-heterocycle diastereomers were converted to chiral pyrrolizines with high diastereoselectivity and pyrrolizine carboxylate was obtained in 54% yield with 90% ee by the removal of chiral auxiliary.

中文翻译：

银(I)促进N-乙烯基-α,β-不饱和硝酮与手性3-Propioloyloxazolidin-2-Ones的环加成和重排合成手性九元N-杂环

通过银(I)催化的[3+2]环加成和N-乙烯基-α,β的[3,3]-重排，以中等至良好的收率制备了多种手性九元N-杂环化合物，具有高非对映选择性-不饱和硝酮和手性 3-propioloyloxazolidin-2-ones。实验研究表明，银催化剂促进了环加成和重排过程，九元N-杂环的立体化学通过手性恶唑烷酮辅助剂的[3,3]-重排通过船状过渡态进行控制。此外，得到的九元N-杂环非对映异构体被转化为具有高非对映选择性的手性吡咯嗪，通过去除手性助剂以54%的收率和90%的ee得到吡咯嗪羧酸盐。

更新日期：2021-11-26

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