The control of regioselectivity in Heck-type reaction of unactivated alkenes represents a longstanding challenge due to several detachable hydrogens in β–H elimination step, which generally afford either one specific regioisomer or a mixture. Herein, a copper-catalyzed intermolecular Heck-type reaction of unactivated alkenes and N-fluoro-sulfonamides with divergent regioselectivities is reported. The complete switch of regioselectivity mainly depends on the choice of different additives. Employment of alcohol solvent gives access to vinyl products, while the addition of carboxylate leads to the formation of allylic products. In addition, exclusion of these two promoting factors results in β-lactams via a C–N reductive elimination. This protocol shows a broad substrate scope for both alkenes and structurally diverse N-fluoro-sulfonamides, producing the corresponding products with excellent regio- and stereoselectivities. Further control experiments and DFT calculations provide in-depth insights into the reaction mechanism, highlighting the distinct effect of the additives on a bidentate auxiliary-stabilized Cu(III) intermediate.

由于在 β-H 消除步骤中存在几个可分离的氢，因此控制未活化烯烃的 Heck 型反应中的区域选择性是一项长期挑战，这些氢通常提供一种特定的区域异构体或混合物。在此，铜催化的未活化烯烃和N的分子间 Heck 型反应报道了具有不同区域选择性的-氟磺酰胺。区域选择性的完全转换主要取决于不同添加剂的选择。使用醇溶剂可以获得乙烯基产物，而添加羧酸盐会导致形成烯丙基产物。此外，排除这两种促进因子会通过 C-N 还原消除产生 β-内酰胺。该协议显示了烯烃和结构多样的N-氟磺酰胺的广泛底物范围，产生了具有优异区域选择性和立体选择性的相应产品。进一步的控制实验和 DFT 计算提供了对反应机理的深入了解，突出了添加剂对双齿辅助稳定的 Cu(III) 中间体的明显影响。