A RhII-Catalyzed [4 + 3]-Cycloaddition via the Stereoselective Cyclopropanation of Vinyl Allenes En Route to Oxepino[b]indoles and Subsequent Elaboration to Spirooxindole Frameworks

IF 4.9 1区化学 Q1 CHEMISTRY, ORGANIC

Organic Letters Pub Date : 2025-05-01 DOI:10.1021/acs.orglett.5c01329

Jiyoon Kim, Kevin X. Rodriguez, Kaitlyn E. Eckert, Allen G. Oliver, Brandon L. Ashfeld

引用次数: 0

Abstract

Oxepino[b]indoles were obtained in good to excellent yields employing a [4 + 3]-cycloaddition initiated by a stereo- and regioselective, Rh^II-catalyzed cyclopropanation between a vinyl allene and diazooxindole to afford an intermediate cyclopropyl allene that engaged the oxindole carbonyl in a spontaneous hetero-[3,3]-rearrangement. A survey of functional group tolerance revealed a diverse array of substrates amenable to oxepino[b]indole formation. In addition to the intriguing architecture of the cycloadducts, exposure to either Brønsted acid or base enables the assembly of functionalized spirroxindoles via the unusual conversion of a 5–7 fused ring system to a 5–5 spirocycle.

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rhii催化的[4 + 3]-乙烯基烯的立体选择性环丙化加成制Oxepino[b]吲哚和随后的螺旋吲哚框架的精化

通过在乙烯基烯烯和重氮唑新哚之间进行立体选择性和区域选择性的[4 + 3]环加成反应，生成中间环丙基烯烯，与新哚羰基进行自发的杂[3,3]重排，得到了Oxepino[b]吲哚，收率很高。一项对功能基耐受性的调查显示，多种底物可适应oxepino[b]吲哚的形成。除了环加合物有趣的结构外，暴露于br - nsted酸或碱中，通过不寻常的将5-7熔合环系统转化为5-5螺旋环，可以组装功能化的螺旋化合物。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Organic Letters 化学-有机化学

CiteScore

9.30

自引率

11.50%

发文量

1607

审稿时长

1.5 months

期刊介绍： Organic Letters invites original reports of fundamental research in all branches of the theory and practice of organic, physical organic, organometallic,medicinal, and bioorganic chemistry. Organic Letters provides rapid disclosure of the key elements of significant studies that are of interest to a large portion of the organic community. In selecting manuscripts for publication, the Editors place emphasis on the originality, quality and wide interest of the work. Authors should provide enough background information to place the new disclosure in context and to justify the rapid publication format. Back-to-back Letters will be considered. Full details should be reserved for an Article, which should appear in due course.