Phosphine-Mediated de Novo Arylamidation of α-Allylic Allenoates and Isocyanates via Bicyclo[3.1.0]hexene Access to Aryl Amides.

IF 4.9 1区化学 Q1 CHEMISTRY, ORGANIC

Organic Letters Pub Date : 2025-06-16 DOI:10.1021/acs.orglett.5c01354

Xuling Pan,You Huang

引用次数: 0

Abstract

Amides are highly valuable structural units in pharmaceuticals and organic materials. Despite enormous progress in this field, de novo construction of aryl amides is underdeveloped. Here we present a phosphine-mediated arylamidine of α-allylic-substituted allenoates with isocyanates. This methodology features broad substrate scope, simple experimental operation, high efficiency, and good functional group tolerance. Isolation experiments on bicyclo[3.1.0]hexene, coupled with deuterium experiments, clarify a stepwise pathway involving ring-opening and aromatization processes, with the ring-opening step identified as crucial for achieving the aryl amides. The synthetic utility of this protocol has been further demonstrated by carrying out several downstream transformations and a concise formal synthesis of the benzene-1,3,5-tricarboxamide (BTA) molecule.

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膦介导的双环[3.1.0]己烯获取芳基酰胺的α-烯丙酸酯和异氰酸酯的新芳基酰胺化。

酰胺是药物和有机材料中非常有价值的结构单元。尽管在这一领域取得了巨大的进展，但芳基酰胺的从头构建还不发达。在这里，我们提出了一个膦介导的α-烯丙基取代异氰酸酯的芳基酰胺。该方法具有底物范围广、实验操作简单、效率高、官能团容忍度好等特点。双环[3.1.0]己烯的分离实验，结合氘实验，阐明了包括开环和芳构化过程的逐步途径，其中开环步骤被认为是获得芳基酰胺的关键步骤。通过进行几个下游转化和苯-1,3,5-三羧基酰胺（BTA）分子的简洁形式合成，进一步证明了该方案的合成效用。

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.