Cao Dawei, Xia Shumei, Li Lijuan, Zeng Huiying, Li Chao-Jun
Key Laboratory of Green and High-end Utilization of Salt Lake Resources, Qinghai Technology Research and Development Center of Comprehensive Utilization of Salt Lakes Resources, Qinghai Institute of Salt Lakes, Chinese Academy of Sciences, Xining, Qinghai 810008, China.
Department of Chemistry and FRQNT Centre for Green Chemistry and Catalysis, McGill University, Montreal, Quebec H3A 0B8, Canada.
Org Lett. 2024 Aug 2;26(30):6418-6423. doi: 10.1021/acs.orglett.4c02207. Epub 2024 Jul 24.
Deoxygenation of epoxides into alkenes is one of the most important strategies in organic synthesis, biomass conversions, and medicinal chemistry. Although metal-catalyzed direct deoxygenation provides one of the most commonly encountered protocols for the conversion of epoxides to alkenes, the requirement of expensive catalysts and extra reductants has largely limited their universal applicability. Herein, we report an efficient PPh-promoted metal-free strategy for deoxygenation of epoxides to generate alkene derivatives. The success of deoxyalkenylation of epoxides bearing a wide range of functional groups to give terminal, 1,1-disubstituted, and 1,2-disubstituted alkenes manifests the powerfulness and versatility of this strategy. Moreover, gram-scale synthesis with excellent yield and modification of biologically active molecules exemplifies its generality and practicability.
环氧化合物脱氧生成烯烃是有机合成、生物质转化和药物化学中最重要的策略之一。尽管金属催化的直接脱氧为环氧化合物转化为烯烃提供了最常见的方法之一，但昂贵的催化剂和额外的还原剂的需求在很大程度上限制了它们的普遍适用性。在此，我们报道了一种高效的由三苯基膦促进的无金属策略，用于环氧化合物脱氧以生成烯烃衍生物。带有各种官能团的环氧化合物脱氧烯基化成功生成末端烯烃、1,1-二取代烯烃和1,2-二取代烯烃，这体现了该策略的强大功能和通用性。此外，克级规模的合成具有优异的产率以及生物活性分子的修饰例证了其通用性和实用性。
