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通过集成光催化从羧酸、醇和烷烃合成模块化烯烃

Modular alkene synthesis from carboxylic acids, alcohols and alkanes via integrated photocatalysis.

作者信息

Zeng Hao, Yin Ruize, Zhao Yu, Ma Jun-An, Wu Jie

机构信息

Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Binhai New City, P. R. China.

Department of Chemistry, National University of Singapore, Singapore, Republic of Singapore.

出版信息

Nat Chem. 2024 Nov;16(11):1822-1830. doi: 10.1038/s41557-024-01642-6. Epub 2024 Sep 27.

Abstract

Alkenes serve as versatile building blocks in diverse organic transformations. Despite notable advancements in olefination methods, a general strategy for the direct conversion of carboxylic acids, alcohols and alkanes into alkenes remains a formidable challenge owing to their inherent reactivity disparities. Here we demonstrate an integrated photochemical strategy that facilitates a one-pot conversion of these fundamental building blocks into alkenes through a sequential C(sp)-C(sp) bond formation-fragmentation process, utilizing an easily accessible and recyclable phenyl vinyl ketone as the 'olefination reagent'. This practical method not only offers an unparalleled paradigm for accessing value-added alkenes from abundant and inexpensive starting materials but also showcases its versatility through various complex scenarios, including late-stage on-demand olefination of multifunctional molecules, chain homologation of acids and concise syntheses of bioactive molecules. Moreover, initiating from carboxylic acids, alcohols and alkanes, this protocol presents a complementary approach to traditional olefination methods, making it a highly valuable addition to the research toolkit for alkene synthesis.

摘要

烯烃在各种有机转化中作为通用的结构单元。尽管烯烃化方法取得了显著进展,但由于羧酸、醇和烷烃固有的反应性差异,将它们直接转化为烯烃的通用策略仍然是一项艰巨的挑战。在此,我们展示了一种集成光化学策略,该策略通过连续的C(sp)-C(sp)键形成-断裂过程,利用易于获得且可回收的苯基乙烯基酮作为“烯烃化试剂”,促进这些基本结构单元一锅法转化为烯烃。这种实用方法不仅为从丰富且廉价的起始原料获取增值烯烃提供了无与伦比的范例,还通过各种复杂场景展示了其通用性,包括多功能分子的后期按需烯烃化、酸的链同系化以及生物活性分子的简洁合成。此外,该方案从羧酸、醇和烷烃出发,为传统烯烃化方法提供了一种补充方法,使其成为烯烃合成研究工具包中极具价值的补充。

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