Being key parts in innumerable catalytic reactions, until this day, electrophiles serve almost exclusively two general purposes through their functional group: first, locating the bond-forming site at the corresponding substrate and second, providing the electronic bias for entering the catalytic cycle. Beyond that, such conventional electrophiles are passive throughout the reaction rendering the functional group and the corresponding prior synthetic efforts to install it highly sacrificial. This work^[1] introduces the concept of non-innocent electrophiles. In contrast to conventional electrophiles such as commonly used organic halides or sulfonates, this new class of multifunctional electrophiles actively participates in the reaction beyond the classical paradigm, thus providing extended reactive opportunities. The concept was used as a platform for the development of exogenous base-free coupling reactions and provided a general solution to the ‘base problem’, a longstanding challenge in cross-coupling chemistry. Considered an inherent requisite for catalytic turnover, the use of (super)stoichiometric amounts of base in transition metal-catalyzed coupling reactions simultaneously limits the accessible chemical space, is suboptimal in terms of resource efficiency, and typically renders reaction conditions heterogeneous which affects reproducibility, scale-up campaigns, and the implementation of emerging technologies, e.g. flow chemistry or high-throughput experimentation.^[1] Therefore, a general approach that eludes the need for exogenous bases in coupling reactions would be beneficial in various aspects. In summary, the study confirmed the hypothesis and diisopropylcarbamates as well as tert-butyl carbonates were found to release a competent base after oxidative addition. Notably, this catalytic release mechanism generates the base on-demand as it is coupled to the oxidative addition of the catalyst, and by that establishes self-sustaining catalytic systems with intrinsic self-regulation and efficiently overrides the deleterious effects caused by the use of an exogenous base. As a result multiple coupling reactions (9 distinct classes of coupling reactions) which traditionally rely on the addition of (super)stoichiometric base could be turned into exogenous base-free, homogeneous processes, that were compatible with base-sensitive functional groups. Importantly, C‒H/C‒O coupling scenarios proved feasible representing a promising avenue for the development of  more sustainable catalytic platforms. Furthermore, the advantageous features of non-innocent electrophiles over conventional electrophiles were demonstrated in multiple relevant applications, i.e. miniaturization, reactivity sensing and reaction discovery. For example, a micromole-scale fluorescence-based assay for reaction discovery was developed that reliably and rapidly detects reactivity requiring minimal amounts of materials and in which a common benchtop UV-lamp is sufficient for reactivity detection allowing for naked-eye analysis of the samples. This led to the discovery of a novel Ni-catalyzed exogenous base-free deoxygenation reaction of aryl carbamates using isopropanol as a benign reductant.