We report a user‐friendly approach for the decarboxylative formation of stereodefined and complex tri‐ and tetra‐substituted olefins from vinyl cyclic carbonates and amines as radical precursors. The protocol relies on easy photo‐initiated α‐amino‐radical formation followed by addition onto the double bond of the substrate resulting in a sequence involving carbonate ring‐opening, double bond relay, CO2 extrusion and finally O‐protonation. The developed protocol is efficient for both mismatched and matched polarity substrate combinations, and the scope of elaborate stereodefined olefins that can be forged including drug‐functionalized derivatives is wide, diverse and further extendable to other types of heterocyclic and radical precursors. Mechanistic control reactions show that the decarboxylation step is a key driving force towards product formation, with the initial radical addition under steric control.

中文翻译：

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一种简便的自由基脱羧合成立体全碳四取代烯烃的方法

我们报告了一种用户友好的方法，用于从乙烯基环状碳酸酯和胺作为自由基前体脱羧形成立体定义的复杂三取代和四取代烯烃。该方案依赖于简单的光引发α-氨基自由基形成，然后加成到底物的双键上，从而产生涉及碳酸酯开环、双键中继、CO2挤出和最终O-质子化的序列。所开发的方案对于不匹配和匹配的极性底物组合均有效，并且可以锻造的精细立体烯烃的范围（包括药物功能化衍生物）广泛、多样，并可进一步扩展到其他类型的杂环和自由基前体。机械控制反应表明，脱羧步骤是产物形成的关键驱动力，初始自由基加成处于空间控制下。