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铑催化的烯基异氰酸酯与炔烃的[2 + 2 + 2]环加成反应

Rhodium-catalyzed [2 + 2 + 2] cycloaddition of alkenyl isocyanates and alkynes.

作者信息

Yu Robert T, Rovis Tomislav

机构信息

Department of Chemistry, Colorado State University, Fort Collins, CO 80523, USA.

出版信息

J Am Chem Soc. 2006 Mar 8;128(9):2782-3. doi: 10.1021/ja057803c.

DOI:10.1021/ja057803c
PMID:16506740
Abstract

A rhodium(I)-catalyzed [2 + 2 + 2] cycloaddition between alkenyl isocyanates and alkynes has been developed. Heating a mixture of an alkenyl isocyanate and a symmetrical internal alkyne in the presence of [Rh(ethylene)2Cl]2/P(4-OMe-C6H4)3 in toluene delivers substituted indolizinones and quinolizinones. Depending on the substrates, a rare fragmentation of the isocyanate unit can be involved within the cycloaddition process to furnish a vinylogous amide embedded in the indolizinone.

摘要

已开发出一种铑(I)催化的烯基异氰酸酯与炔烃之间的[2 + 2 + 2]环加成反应。在甲苯中,[Rh(乙烯)₂Cl]₂/P(4-甲氧基-C₆H₄)₃存在下,加热烯基异氰酸酯和对称内炔的混合物,可得到取代的中氮茚酮和喹嗪酮。根据底物的不同,在环加成过程中可能会发生异氰酸酯单元罕见的断裂,从而形成嵌入中氮茚酮中的烯醇酰胺。

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