Carbonyl cross-metathesis via deoxygenative gem-di-metal catalysis
Carbonyl cross-metathesis via deoxygenative gem-di-metal catalysis
复制标题
DOI：
10.1038/s41557-023-01333-8
复制
发表时间：
2023-09
期刊：
影响因子：
21.8
通讯作者：
Lumin Zhang;David A. Nagib
中科院分区：
文献类型：
--
作者：
Lumin Zhang;David A. Nagib
羰基和烯烃是一类用途广泛的官能团，它们的反应性是有机合成的基础。两个羰基选择性地结合形成一个烯烃-羰基交叉复分解-将是它们交换的有价值的工具。然而，这一重要的合成挑战仍未得到解决。尽管烯烃/烯烃和烯烃/羰基交叉复分解反应是已知的，但缺乏用于两种羰基化合物的脱氧交叉偶联的类似方法。在这里，我们报告了一对无偏羰基交叉复分解的策略，允许醛与另一种醛或酮化学和立体选择性地结合。这些温和的催化方法是由地球上丰富的金属盐促进的，并且能够通过两种不同的机制快速获得前所未有的广泛的Z-或E-烯烃，这两种不同的机制需要瞬时生成（1）卡宾和叶立德（通过Fe催化）或（2）双重亲核的双金属化合物（通过Cr催化）。
Carbonyls and alkenes are versatile functional groups, whose reactivities are cornerstones of organic synthesis. The selective combination of two carbonyls to form an alkene—a carbonyl cross-metathesis—would be a valuable tool for their exchange. Yet, this important synthetic challenge remains unsolved. Although alkene/alkene and alkene/carbonyl cross-metathesis reactions are known, there is a lack of analogous methods for deoxygenative cross-coupling of two carbonyl compounds. Here we report a pair of strategies for the cross-metathesis of unbiased carbonyls, allowing an aldehyde to be chemo- and stereoselectively combined with another aldehyde or ketone. These mild, catalytic methods are promoted by earth-abundant metal salts and enable rapid access to an unprecedentedly broad range of eitherZ- orE-alkenes by two distinct mechanisms—entailing transiently generated (1) carbenes and ylides (via Fe catalysis) or (2) doubly nucleophilicgem-di-metallics (via Cr catalysis).