Sustainable Knowledge-Driven Approaches in Transition-Metal-Catalyzed Transformations.

The sustainable synthesis of relevant scaffolds for their use in the pharmaceutical, agrochemical, and materials sectors constitutes one of the most urgent challenges that the chemical community needs to overcome. In this context, the development of innovative and more efficient catalytic processes based on a fundamental understanding of the underlying reaction mechanisms remains a largely unresolved challenge for academic and industrial chemists. Herein, selected examples of computational and experimental knowledge-driven approaches for the rational design of transition-metal-catalyzed transformations are discussed.

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

Despite the known nucleophilic nature of [M(CF ) ] (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(CF ) ] 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.

Beyond the traditional roles of Ag in catalysis: the transmetalating ability of organosilver(i) species in Pd-catalysed reactions.

Silver salts are one of the most widely used additives in Pd-catalysed transformations. Apart from acting as a halide scavenger and/or an external oxidant, over the past decade it has been revealed that silver salts can play other roles such as a C-H activation promoter or decarboxylating agent, generating organosilver(i) species. These nucleophiles can promote innovative transformations by reacting with PdII intermediates through a transmetalation step.

New Vistas in Transmetalation with Discrete "AgCF " Species: Implications in Pd-Mediated Trifluoromethylation Reactions.

This work describes the employment of discrete "AgCF " complexes as efficient transmetalating agents to Pd to surmount overlooked challenges related to the transmetalation step in Pd-catalyzed trifluoromethylation processes. We report the participation of a unique silver ate (Cs)[Ag(CF ) ] complex, under stoichiometric and catalytic conditions, in the unprecedented one-pot formation of PhCF using PhI as starting material. Moreover, we show that the transmetalation step, which is often ignored in these transformations, can also determine the success or failure of the coupling process.

Catalytic Nitrene Transfer To Alkynes: A Novel and Versatile Route for the Synthesis of Sulfinamides and Isothiazoles.

A novel transformation is reported for the reaction of terminal or internal alkynes with the nitrene precursor PhI=NTs (Ts=p-toluenesulfonyl) in the presence of catalytic amounts of Tp Cu(NCMe) (Tp =hydrotris(3,4,5-tribromo-pyrazolylborate). Two products containing an imine functionality have been isolated from the reaction mixtures, identified as sulfinamides and isothiazoles. The former correspond to the formal reduction of the sulfone group into sulfoxide, whereas the latter involves the insertion of an alkyne carbon atom into the aromatic ring of the N-tosyl moiety.