Complex molecule synthesis by electrocatalytic decarboxylative cross-coupling

Silver Surface-Assisted Dehydrobrominative Cross-Coupling between Identical Aryl Bromides

“…When it comes to the effect of silver substrate, it not only serves as catalyst for the generation of C-radicals intermediates but also interacts with these highly reactive intermediates and alters their stability and reactivity, ultimately determining the selectivity of the intermolecular C–C coupling reactions. Such an effect of transition metals on radical-based coupling reactions have been previously observed and utilized to achieve highly selective radial-radical cross-coupling in wet chemistry. , …”

“…Such an effect of transition metals on radical-based coupling reactions have been previously observed and utilized to achieve highly selective radial-radical cross-coupling in wet chemistry. 49,50 In the following, we discuss the kinetic profiles of the intermolecular aryl−aryl coupling in order to provide a kinetic understanding of selective om-cross-coupling. The intermolecular aryl−aryl coupling of TBPB is a complex consecutive/ parallel reaction that consists of cleavage of the meta-C−H bond of debrominated TBPB and subsequent C−C bond formation between two different species (om-cross-coupling) or two identical species (mm-coupling).…”

Simplified Modular Access to Enantiopure 1,2-Aminoalcohols via Ni-Electrocatalytic Decarboxylative Arylation

“…The pursuit of a reliable means to access the 2-amino-1-arylethanol unit in high enantiopurity via modular cross-coupling was built off of prior studies from this lab, specifically, the recently disclosed electrochemical decarboxylative alkenylation/arylation uniquely promoted by Ag nanoparticles (AgNPs). , Since Csp 2 –Csp 3 bonds are ubiquitous across natural products and pharmacophores, this transformation is highly useful for the rapid and modular construction of carbon skeletons from readily available carboxylic acids and alkynyl/aryl halides. The feasibility of controlling the stereochemistry in this radical-based cross-coupling was supported by the recent disclosure of second-generation doubly decarboxylative coupling, where careful selection of building block structures as well as reaction conditions rendered the alkyl–alkyl bond formation highly diastereoselective . Notably, Ley auxiliary-based RAE 6 (Figure A) was used for the highly stereoselective synthesis of ent -SF2768 and complanine, which set the stage for our exploration in the context of diastereoselective arylation.…”

“…As a result, the current approach provides a much simpler and more intuitive avenue. For example, the simple derivatization of the selected coupling products shown in Figure 3 led to medicinally useful building blocks (27,28) or a marketed drug (1). Previous routes to synthesize these compounds are much longer, involving numerous reactions that are undesired from both safety (toxic intermediates, hazardous/explosive reagents, high-pressure reaction) and sustainability (precious metal-based hydrogenation) perspectives.…”

Carbon quaternization of redox active esters and olefins by decarboxylative coupling

“…In many cases, quaternary C synthesis can be achieved through such methods. The cross-coupling between two different redox active esters has also been reported but is not generally applicable to quaternary C synthesis ( 8 , 9 ). Here, we show how a single catalyst can mediate regioselective quaternization of C using ubiquitous chemical feedstocks: olefins and carboxylic acids (Fig.…”