Over the past 29 years, Group 10-metal-catalyzed aminations of aryl pseudohalides mainly focusing on triflates and more recently, Knochel's nonaflates, have become fundamental processes in organic synthesis for the formation of C(sp 2 )-N bonds. Given the ubiquitous nature of the Naryl and N-heteroaryl-amine motif in natural products, pharmaceuticals, and fine chemicals, should the status of one or more components of a reaction be altered, a need for the development of new technologies arises, preferably those that are not only environmentally responsible but are also efficient, mild, and general. Couplings with aryl triflates and nonaflates are especially common, notwithstanding the alternative, albeit less reactive, mesylates and tosylates. And while they have some inherent disadvantages (such as instability, environmental toxicity, cost of preparation, and poor atom economy in the making of triflates), they are taken for granted as the two main options available for use in synthetic organic chemistry. Unfortunately, as both contain C(sp 3 )-F bonds, they are technically polyfluorinated alkyl substances (PFASs), reagents that only recently have been flagged for their environmental impact. On the other hand, aryl fluorosulfates, first described more than four decades ago, have thus become increasingly popular as coupling partners, all the more so given the range of processes that now exist for their generation from phenolic starting materials (Scheme 1). Hence, a new process that fulfills all of these criteria may represent a breakthrough in the common utilization of phenol-based electrophiles in cross-coupling research in modern synthetic chemistry. The evolution of new generations of ligands is a recent trend in modern transition metal-catalyzed cross coupling reactions. As examples in this regard, several biaryl phosphines, QPhos-based ligands, as well as Cata-CXium-based ligands have been developed to tackle challenging reactions involving pseudohalides. Additionally, significant advancements have been made with the discovery of ferrocene-based ligands by the Colacot group, and N-heterocyclic carbene (NHC)-based ligands by Hermann, Nolan, and Organ. Nonetheless, the search for alternative monodentate phosphine-based pre-catalysts is still very much ongoing, especially given the differences between their anticipated usage in traditional organic solvents versus use in more environmentally responsible processes, including in water under micellar catalysis conditions. One area that remains underexplored, especially from the green chemistry perspective, is development of metal-containing Oxidative Addition Complexes (OACs). A number of groups have previously prepared palladium-containing OACs, albeit for mechanistic studies. More recently, OACs using biarylphosphines (e.g., Buchwald's Pd-G6 complexes) have been found useful for various applications (Scheme 2A). Carrow has reported studies describing the Pd-OAC formed using Ad3P as a unique ligand to carry out both Suzuki-Miyaura couplings of challenging polyfluoroarylboronic acids, as well as otherwise difficult C-N couplings of aryl halides under mild conditions (Scheme 2B). Especially noteworthy is the work by Colacot et al. who have developed a general Pd-OAC using relatively inexpensive tBu3P as ligand enabling various C-C and C-N cross couplings of aryl halides (Scheme 2C). Prior seminal studies have already established that aryl fluorosulfates function as effective cross-coupling partners using traditional Pd (or Ni) catalysis in aminations 43b and other C-C cross coupling reactions. Nonetheless, catalyst loadings are not only costly but unsustainable (typically run in organic solvents with >2 mol % Pd) when considered for use at scale. Moreover, the very limited substrate scope in each renders these protocols even more worthy of further exploration. Importantly, other factors such as solvent and/or catalyst recycling, and metrics relating to the environmental friendliness of these processes (such as E Factors, 47 PMI, 48 etc.) have rarely been considered. These parameters, yet again, highlight the pressing need for an alternative, far more environmentally attractive and sustainable process for aminations. In addition, significant reaction rate enhancements associated with what are otherwise typically time-consuming processes would also represent a significant advance.