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老方法、新套路:酒精脱氧和C-C键形成的Wolff-Kishner还原反应 2022-01-11
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Synlett 2019; 30(13): 1508-1524
DOI: 10.1055/s-0037-1611853

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Chao-Jun LiJianlin HuangXi-Jie DaiHaining WangNing Chen Wei WeiHuiying ZengJianting TangChenchen LiDianhu ZhuLeiyang Lv

An Old Dog with New Tricks: Enjoin Wolff–Kishner Reduction for Alcohol Deoxygenation and C–C Bond Formations

老方法、新套路:酒精脱氧和C-C键形成的Wolff-Kishner还原反应

Wolff-Kishner 还原反应,最早发现于 20 世纪 10 年代,是通过在强碱性条件下脱氧将羰基转化为亚甲基的基础和有效的反应。一个多世纪以来,人们已采用该典型方法合成了很多有价值的化学产品。该典型化学反应通过可逆形成腙,然后用强碱去质子化,得到 N-阴离子中间体,这种中间体经除氮和质子化作用,生成脱氧产物。通过对这个有一个世纪使用历史的典型羰基脱氧的化学机理进行深入研究,我们预测并随后开发了两种史无前例的新化学转化方法:a)酒精脱氧和b)通过各种亲电子试剂(包括 Grignard 型反应、共轭加成、烯化和各种交联反应)的 C-C 键形成。

The Wolff–Kishner reduction, discovered in the early 1910s, is a fundamental and effective tool to convert carbonyls into methylenes via deoxygenation under strongly basic conditions. For over a century, numerous valuable chemical products have been synthesized by this classical method. The reaction proceeds via the reversible formation of hydrazone followed by deprotonation with the strong base to give an N-anionic intermediate, which affords the deoxygenation product upon denitrogenation and protonation. By examining the mechanistic pathway of this century old classical carbonyl deoxygenation, we envisioned and subsequently developed two unprecedented new types of chemical transformations: a) alcohol deoxygenation and b) C–C bond formations with various electrophiles including Grignard-type reaction, conjugate addition, olefination, and diverse cross-coupling reactions.


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本刊是一份国际期刊,以个性化短评和初步简报的形式报告有机合成化学的研究成果和当前趋势。它涵盖了所有涉及有机合成的科研领域,包括催化、有机金属、医药、生物学和光化学,也包括其他相关学科,同时也可通过其发表科学原始数据。