Photocatalyzed anti-Markovnikov addition of carboxylic acids to alkenes: ionic mechanism under radical conditions

IF 4.6 1区化学 Q1 CHEMISTRY, ORGANIC

Organic Chemistry Frontiers Pub Date : 2025-01-13 DOI:10.1039/d4qo02280g

Dmitry L Lipilin, Mikhail O Zubkov, Mikhail Kosobokov, Alexander Dilman

引用次数: 0

Abstract

Since the advent of photocatalysis, the radical addition to alkenes has become one of the most fruitful processes for building up the molecular complexity. Herein we describe a novel approach to photocatalyzed addition to alkenes, in which both new C–O and C–H bonds are formed by an ionic, rather than conventional radical mechanism. This occurs due to two consecutive radical-polar crossover events, providing the generation of both radical cation and carbanion species during the reaction. Such a transformation is demonstrated by the acridine-catalyzed addition of carboxylic acids to styrenes. Unique mechanism allows to carry out the reaction in the absence of additives, and also to reverse the regioselectivity of conventional ionic addition to alkenes.

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自光催化技术问世以来，烯烃的自由基加成已成为增加分子复杂性的最富有成效的过程之一。在本文中，我们介绍了一种光催化烯烃加成的新方法，在这种方法中，新的 C-O 和 C-H 键都是通过离子而非传统的自由基机制形成的。这是由于两个连续的自由基-极性交叉事件，在反应过程中产生了自由基阳离子和碳阴离子。吖啶催化的苯乙烯与羧酸的加成反应证明了这种转变。独特的机理使得该反应可以在没有添加剂的情况下进行，而且还能逆转烯烃传统离子加成反应的区域选择性。

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 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.