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金催化的 1,6-二炔基碳酸酯到苯并[b]菲的级联环化反应,涉及氧杂碳翁离子中间体的芳基化和脱羧基醚化。

Gold-catalyzed cascade cyclizations of 1,6-diynyl carbonates to benzo[b]fluorenes involving arylation of oxocarbenium ion intermediates and decarboxylative etherification.

机构信息

State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, PR China.

出版信息

Angew Chem Int Ed Engl. 2012 Jun 25;51(26):6493-7. doi: 10.1002/anie.201201799. Epub 2012 May 16.

DOI:10.1002/anie.201201799
PMID:22593083
Abstract

Rearranged: The described gold-catalyzed cycloisomerizations give access to highly substituted benzo[b]fluorenes under mild reaction conditions (see scheme). Experimental results indicate that the in situ formed oxocarbenium ion intermediates, derived from gold-catalyzed 3,3-rearrangement and 6-endo-dig cyclization, undergo intramolecular arylation and subsequent decarboxylative etherification to furnish the final ether products.

摘要

重排

所描述的金催化环异构化反应在温和的反应条件下提供了高度取代的苯并[b]菲(见方案)。实验结果表明,源自金催化的 3,3-重排和 6-endo-环化的原位形成的氧杂卡宾离子中间体经历分子内芳基化和随后的脱羧基醚化,以提供最终的醚产物。

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