Photoredox copper-catalyzed regioselective syntheses of allenols via HAT-mediated propargyl radical generation

IF 4.6 1区化学 Q1 CHEMISTRY, ORGANIC

Organic Chemistry Frontiers Pub Date : 2024-09-18 DOI:10.1039/d4qo01245c

Wenyao Li, Hao Yu, Shengming Ma

引用次数: 0

Abstract

Selectivity control of the reactions of propargylic and/or allenylic radicals remains particularly elusive. Here, a visible light-mediated Cu-catalyzed protocol for the highly selective syntheses of tri- and tetra-substituted allenols from alkynol derivatives has been developed. Synthetic potentials of the products have been demonstrated. The control experiments, Stern-Volmer quenching, and cyclic voltammetry studies support a reaction pathway involving the generation of allenyl radicals via photo-mediated N-O bond scission, intramolecular 1,5-HAT process, the resonance to propargylic radicals, and coupling. Non-common intramolecular 1,6-HAT process has also been observed.

查看原文本刊更多论文

通过 HAT 介导的丙炔基生成光氧铜催化的烯醇的区域选择性合成

丙炔基和/或烯酰基反应的选择性控制仍然特别难以实现。在此，我们开发了一种可见光介导的铜催化方案，用于从炔醇衍生物高选择性地合成三代和四代烯醇。产品的合成潜力已得到证实。对照实验、Stern-Volmer 淬火和循环伏安法研究都支持通过光介导的 N-O 键裂解、分子内 1,5-HAT 过程、与丙炔自由基的共振和耦合生成烯基自由基的反应途径。此外，还观察到了非常见的分子内 1,6-HAT 过程。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文求助全文

来源期刊

Organic Chemistry Frontiers CHEMISTRY, ORGANIC-

CiteScore

7.90

自引率

11.10%

发文量

686

审稿时长

1 months

期刊介绍： Organic Chemistry Frontiers is an esteemed journal that publishes high-quality research across the field of organic chemistry. It places a significant emphasis on studies that contribute substantially to the field by introducing new or significantly improved protocols and methodologies. The journal covers a wide array of topics which include, but are not limited to, organic synthesis, the development of synthetic methodologies, catalysis, natural products, functional organic materials, supramolecular and macromolecular chemistry, as well as physical and computational organic chemistry.