α-Tertiary aliphatic amides are key elements in organic molecules, which are abundantly present in natural products, pharmaceuticals, agrochemicals, and functional organic materials. Enantioconvergent alkyl-alkyl bond-forming process is one of the most straightforward and efficient, yet highly challenging ways to build such stereogenic carbon centers. Herein, we report an enantioselective alkyl-alkyl cross-coupling between two different alkyl electrophiles to access α-tertiary aliphatic amides. With a newly-developed chiral tridentate ligand, two distinct alkyl halides were successfully cross-coupled together to forge an alkyl-alkyl bond enantioselectively under reductive conditions. Mechanistic investigations reveal that one alkyl halides exclusively undergo oxidative addition with nickel versus in-situ formation of alkyl zinc reagents from the other alkyl halides, rendering formal reductive alkyl-alkyl cross-coupling from easily available alkyl electrophiles without preformation of organometallic reagents.

α-叔脂肪族酰胺是有机分子中的关键元素，大量存在于天然产物、药物、农用化学品和功能性有机材料中。对映聚合的烷基-烷基键形成过程是构建此类立体碳中心的最直接、最有效但最具挑战性的方法之一。在此，我们报告了两种不同的烷基亲电子试剂之间的对映选择性烷基-烷基交叉偶联以获得 α-叔脂肪族酰胺。使用新开发的手性三齿配体，两个不同的烷基卤化物成功地交叉偶联在一起，在还原条件下对映选择性地形成烷基-烷基键。