Photoredox/Cobalt Dual-Catalyzed Regioselective Hydroalkoxylation of 1,3-Dienes with Alcohols

IF 4.7 1区 化学 Q1 CHEMISTRY, ORGANIC
Bei Chen, Zhimeng Song, Yukun Chen, Xingru Yan, Ge Zhang, Qian Zhang
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引用次数: 0

Abstract

Catalytic hydroalkoxylation of alkenes with oxygen-nucleophiles is of great interest and importance but remains an under developing task in synthetic chemistry. Here, we developed a photoredox and Co-catalyzed regioselective hydroalkoxylation of 1,3-dienes with alcohols, which enables efficient access to valuable allylic ethers in good to excellent yields. The reaction features mild conditions, good functional group tolerance, and wide substrate scope. Application of this rection to late-stage functionalization of relatively complex natural products and bioactive molecules further increases the utility of the developed methodology. Mechanistic studies suggest that the reaction underwent a CoH-mediated hydrogen atom transfer (HAT) to 1,3-diene, followed by a radical-polar crossover process involving nucleophilic displacement of allylic cobalt(IV) with free alcohols. This reaction is an important complement to the arsenal of transition-metal-catalyzed hydroalkoxylation of alkenes, providing a new strategy to deliver valuable allylic ethers.
光氧化还原/钴双催化1,3-二烯与醇的区域选择性氢烷氧基化
烯烃与亲氧核试剂的催化氢烷氧基化是合成化学中一个非常重要的研究方向,但仍是一个有待发展的课题。在这里,我们开发了一种光氧化还原和共催化的1,3-二烯与醇的区域选择性氢烷氧基化反应,它能够以良好的收率高效地获得有价值的烯丙醚。该反应具有条件温和、官能团耐受性好、底物范围广等特点。将此方法应用于相对复杂的天然产物和生物活性分子的后期功能化,进一步增加了所开发方法的实用性。机理研究表明,该反应经历了coh介导的氢原子转移(HAT)到1,3-二烯,随后是自由基-极性交叉过程,包括游离醇的亲核取代烯丙基钴(IV)。该反应是对过渡金属催化烯烃氢烷氧基化反应的重要补充,提供了一种传递有价值的烯丙醚的新策略。
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来源期刊
Organic Chemistry Frontiers
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.
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