文章基本信息

标题：Light-Driven Metal-Free Direct Deoxygenation of Alcohols under Mild Conditions
本地全文：下载
作者：Dawei Cao ; Zhangpei Chen ; Leiyang Lv 等
期刊名称：iScience
印刷版ISSN：2589-0042
出版年度：2020
卷号：23
期号：8
页码：1-62
DOI：10.1016/j.isci.2020.101419
语种：English
出版社：Elsevier
摘要：SummaryHydroxyl is widely found in organic molecules as functional group and its deprivation plays an inevitable role in organic synthesis. However, the direct cleavage of Csp3-O bond in alcohols with high selectivity and efficiency, especially without the assistance of metal catalyst, has been a formidable challenge because of its strong bond dissociation energy and unfavorable thermodynamics. Herein, an efficient metal-free strategy that enables direct deoxygenation of alcohols has been developed for the first time, with hydrazine as the reductant induced by light. This protocol features mild reaction conditions, excellent functional group tolerance, and abundant and easily available starting materials, rendering selective deoxygenation of a variety of 1° and 2° alcohols, vicinal diols, andβ-1 and evenβ-O-4 models of natural wood lignin. This strategy is also highlighted by its “traceless” and non-toxic by-products N2and H2, as readily escapable gases. Mechanistic studies demonstrated dimethyl sulfide being a key intermediate in this transformation.Graphical AbstractDisplay OmittedHighlights•Metal-free direct deoxygenation of alcohols enabled by light•Traceless non-toxic N2and H2as by-products•Broad substrate scope and wide functional group compatibility•Converting lignin models into simple aromaticsCatalysis; Chemistry; Organic Chemistry.