Metal-free and visible-light-mediated method enables the synthesis of olefins from ketones

Yu Zhang , Xinyu Han , Rongkai Wu , Jinxin Wang , Qiannan Li , Jingchuan Lin , Dingding Xia , Xin Hong , Shoubhik Das , Wei-Dong Zhang
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Abstract

Direct synthesis of olefins continues to attract stellar attention due to the high importance of olefins. In this context, due to the wide availability of ketones, the synthesis of olefins directly from ketones provides a straightforward route. Considering this, olefins synthesis from ketones via the formation of donor/donor type carbenes has been developed which leads to the efficient synthesis of versatile olefins by using a metal-free strategy. This approach features mild reaction conditions and exhibits a broad substrate scope when a biomass-derived solvent as a green reaction media is used. The practical utility of this approach has been demonstrated via late-stage modifications and even by scaling up to 20 ​g scale. At the end, mechanistic investigations and density functional theory studies clearly proved the formation of donor/donor carbenes, and examined the necessity of all the reagents and the effect of light in this system.

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通过无金属和可见光介导的方法从酮合成烯烃
由于烯烃的高度重要性,直接合成烯烃继续吸引着恒星的关注。在这种情况下,由于酮的广泛可用性,直接从酮合成烯烃提供了一个简单的途径。考虑到这一点,酮类通过供体/供体型碳烯的形成合成烯烃的研究得到了发展,从而实现了无金属策略下的高效合成多功能烯烃。当使用生物质衍生溶剂作为绿色反应介质时,该方法具有温和的反应条件和广泛的底物范围。这种方法的实际效用已经通过后期的修改,甚至扩大到20g的规模得到了证明。最后,通过机理研究和密度泛函理论研究,明确证明了给体/给体碳烯的形成,并考察了该体系中所有试剂的必要性和光的影响。
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