Diels-Alder环加成和铑催化C-H炔化反应合成苯胺。

IF 5 1区化学 Q1 CHEMISTRY, ORGANIC

Organic Letters Pub Date : 2025-06-30 DOI:10.1021/acs.orglett.5c02227

Wei Chen, Aohang Liu, Jinwei Huang, Pengfei Yu, Huaxuan Zhang, Huilin Li, Xingang Xie, Gaoyuan Zhao* and Xuegong She*,

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引用次数: 0

摘要

Daphenylline是一种结构复杂的水蚤类生物碱，由于其高度融合的六环[6.6.5.7.6.5]框架和多个立体中心，对合成构成了巨大挑战。本文报道了以已知原料为原料，经过12步高效合成苯胺的方法，包括分子内diols - alder反应、氧化芳构化、rh催化的C-H烷基化和醛醇缩合。我们的方法利用羰基导向的C-H功能化策略，在复杂的五环框架内实现区域选择性炔基化，而不需要强烈协调导向基团。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Total Synthesis of Daphenylline via Diels–Alder Cycloaddition and Rhodium-Catalyzed C–H Alkynylation

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Total Synthesis of Daphenylline via Diels–Alder Cycloaddition and Rhodium-Catalyzed C–H Alkynylation

Daphenylline, a structurally intricate Daphniphyllum alkaloid, poses a formidable synthetic challenge due to its highly fused hexacyclic [6.6.5.7.6.5] framework and multiple stereocenters. Herein, we report an efficient total synthesis of daphenylline in 12 steps from known starting materials, featuring a key intramolecular Diels–Alder reaction, oxidative aromatization, Rh-catalyzed C–H alkynylation, and aldol condensation. Our approach leverages a carbonyl-directed C–H functionalization strategy to achieve regioselective alkynylation within a complex pentacyclic framework without the need for strongly coordinating directing groups.

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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.