Alkanes are an abundant and valuable resource for transformation into value-added fine chemicals. However, selective functionalization of specific C(sp³)–H bonds in alkanes for alkyl-alkyl bond formation is a significant challenge because of their intrinsic inertness and the small differences in reactivity among various C(sp³)–H bonds. Here, we report a silver-catalyzed site-selective C(sp³)–H benzylation of simple alkanes using N-triftosylhydrazones as a convenient carbene precursor, which enables the synthesis of high value-added alkylated aromatics. A one-pot two-step protocol starting from aldehydes was also realized, thereby constituting a formal reductive alkylation of aryl aldehydes by alkanes. Experimental investigations and DFT calculations reveal that the role of the [Tp^Br3Ag]₂ catalyst is 3-fold: it modulates the carbene reactivity, inhibits carbene dimerization, and avoids over insertion of the product. All three aspects are crucial for the success of this first site-selective intermolecular insertion of donor carbenes into C(sp³)–H bonds of simple alkanes.

烷烃是转化为高附加值精细化学品的宝贵资源。但是，由于烷烃固有的惰性以及各种C（sp ³）-H键之间的反应性差异小，因此烷烃中特定的C（sp ³）-H键选择性官能化以形成烷基-烷基键是一项重大挑战。在这里，我们报告使用N的简单烷烃的银催化位点选择性C（sp ³）–H苄基化-triftosylhydrazones作为方便的卡宾前体，可以合成高附加值的烷基化芳烃。还实现了从醛开始的一锅两步方案，从而构成了烷烃对芳基醛的正式还原烷基化。实验研究和DFT计算表明[Tp ^Br3 Ag] ₂催化剂的作用是3倍：它调节卡宾反应性，抑制卡宾二聚作用，并避免产物过度插入。所有这三个方面对于将供体卡宾首次分子间分子插入简单烷烃的C（sp ³）-H键的成功至关重要。