Numerous important transition metal-catalysed reactions rely on stoichiometric quantities of an exogenous base to enable catalytic turnover. Despite playing a fundamental role, the base poses major challenges, such as restricting the accessible chemical space or causing heterogeneous reaction mixtures. Here we introduce a unifying strategy that eliminates the need for an exogenous base through the use of non-innocent electrophiles (NIE), which are equipped with a masked base that is released in a controlled fashion during the reaction. The universal applicability of this concept was demonstrated by turning multiple, traditionally base-dependent, catalytic reactions into exogenous base-free homogeneous processes. Furthermore, the advantageous features of NIEs were demonstrated in multiple applications, such as in a micromole-scale fluorescence-based assay. This led to the discovery of a Ni-catalysed deoxygenation reaction of aryl carbamates using isopropanol as a benign reductant. In a broader context, this work provides a conceptual blueprint for the strategic utilization of NIEs in catalysis.

许多重要的过渡金属催化反应依赖于化学计量数量的外源碱来实现催化周转。尽管发挥了基础性作用，但碱基也带来了重大挑战，例如限制可接近的化学空间或导致多相反应混合物。在这里，我们介绍了一种统一策略，该策略通过使用非无辜亲电试剂 (NIE) 消除了对外源碱基的需求，NIE 配备了在反应过程中以受控方式释放的掩蔽碱基。通过将多个传统上依赖碱基的催化反应转变为外源无碱基均相过程，证明了这一概念的普遍适用性。此外，NIE 的优势特性在多个应用中得到了证明，例如在基于微摩尔级荧光的测定中。这导致发现了使用异丙醇作为良性还原剂的氨基甲酸芳基酯的镍催化脱氧反应。在更广泛的背景下，这项工作为 NIE 在催化中的战略利用提供了概念蓝图。