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新型功能取代的 9-氮杂双环[4.2.1]壬-2,4,7-三烯的钴(I)催化[6π + 2π]-环加成反应合成——β-碳杂胆固醇氧基氮杂环庚烷与炔烃。

Synthesis of New Functionally Substituted 9-Azabicyclo[4.2.1]nona-2,4,7-trienes by Cobalt(I)-Catalyzed [6π + 2π]-Cycloaddition of -Carbocholesteroxyazepine to Alkynes.

机构信息

Laboratory of Catalytic Synthesis, Institute of Petrochemistry and Catalysis, Russian Academy of Sciences, 450075 Ufa, Russia.

出版信息

Molecules. 2021 May 14;26(10):2932. doi: 10.3390/molecules26102932.

Abstract

Catalytic [6π + 2π]-cycloaddition of -carbocholesteroxyazepine with functionally substituted terminal alkynes and 1,4-butynediol was performed for the first time under the action of the Co(acac)(dppe)/Zn/ZnI three-component catalytic system. The reaction gave previously undescribed but promising 9-azabicyclo[4.2.1]nona-2,4,7-trienes (in 79-95% yields), covalently bound to a natural metabolite, cholesterol. The structure of the synthesized azabicycles was confirmed by analysis of one- and two-dimensional (H, C, DEPT C, COSY, NOESY, HSQC, HMBC) NMR spectra.

摘要

首次在 Co(acac)(dppe)/Zn/ZnI 三组分催化体系作用下,进行了β-碳胆固醇氧基氮杂环庚烷与功能取代末端炔和 1,4-丁炔二醇的催化[6π+2π]-环加成反应。该反应以天然代谢产物胆固醇为连接基,生成了之前未见报道但很有前景的 9-氮杂双环[4.2.1]壬-2,4,7-三烯(产率为 79-95%)。通过一维和二维(H、C、DEPT C、COSY、NOESY、HSQC、HMBC)NMR 谱分析,对合成的氮杂环进行了结构确证。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/806b/8156619/3c6bef4ed1de/molecules-26-02932-g001.jpg

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