Late-Stage C(sp2)-C(sp3) Diversification via Nickel Oxidative Addition Complexes.

Herein, we describe nickel oxidative addition complexes (Ni-OACs) of drug-like molecules as a platform to rapidly generate lead candidates with enhanced C(sp3) fraction. The potential of Ni-OACs to access new chemical space has been assessed not only in C(sp2)-C(sp3) couplings but also in additional bond formations without recourse to specialized ligands and with improved generality when compared to Ni-catalyzed reactions. The development of an automated diversification process further illustrates the robustness of Ni-OACs, thus offering a new gateway to expedite the design-make-test-analyze (DMTA) cycle in drug discovery.

Ring Walking Mediated by Ni-Ni Species as a Vehicle for Enabling Distal C(sp2)-H Functionalization of Aryl Pivalates.

Herein, we report the utilization of Ni-Ni species as a manifold for enabling a "ring-walking" event by dynamic translocation of the metal center over the arene backbone. Experimental and computational studies support a translocation occurring via a 1,2-hydride shift. The synthetic applicability of the method is illustrated in a series of C-C bond formations that occur at distal C(sp2)-H sites of simple aryl pivalates.

Room-Temperature-Stable Magnesium Electride via Ni(II) Reduction.

Herein, we report the synthesis of highly reduced bipyridyl magnesium complexes and the first example of a stable organic magnesium electride supported by quantum mechanical computations and X-ray diffraction. These complexes serve as unconventional homogeneous reductants due to their high solubility, modular redox potentials, and formation of insoluble, non-coordinating byproducts. The applicability of these reductants is showcased by accessing low-valent (bipy)2Ni(0) species that are challenging to access otherwise.

Ni(I)-Alkyl Complexes Bearing Phenanthroline Ligands: Experimental Evidence for CO2 Insertion at Ni(I) Centers.

Although the catalytic carboxylation of unactivated alkyl electrophiles has reached remarkable levels of sophistication, the intermediacy of (phenanthroline)Ni(I)-alkyl species-complexes proposed in numerous Ni-catalyzed reductive cross-coupling reactions-has been subject to speculation. Herein we report the synthesis of such elusive (phenanthroline)Ni(I) species and their reactivity with CO2, allowing us to address a long-standing question related to Ni-catalyzed carboxylation reactions.

Weakly Coordinated Cobaltacycles: Trapping Catalytically Competent Intermediates in Cp*CoIII Catalysis.

Herein, we disclose the synthesis of metallacyclic Cp*CoIII complexes containing weakly chelating functional groups. We have employed these compounds not only as an exceptional platform for accessing some of the most widely invoked transient intermediates in C-H functionalization processes but also as competent catalysts in different Cp*Co-catalyzed transformations, including a benchmark coupling reaction.

Exploring the Role of Coinage Metalates in Trifluoromethylation: A Combined Experimental and Theoretical Study.

Despite the known nucleophilic nature of [M(CF3 )2 ]- (M=Cu, Ag, Au) complexes, their participation in trifluoromethylation reactions of aryl halides remains unexplored. Here, for the first time, selective access to a [Cu(CF3 )2 ]- species is reported, which is ubiquitous in Cu-mediated trifluoromethylations, and we rationalize its complex mechanistic scenario as well as its behavior compared to its silver and gold congeners through a combination of experimental and computational approaches.