Alkene Dialkylation via Triple Radical Sorting

Published: Nov. 21, 2023

The development of bimolecular homolytic substitution (SH2) catalysis has expanded cross-coupling logic by enabling the selective merger any primary radical with secondary or tertiary via a sorting mechanism. SH2 can be used to merge common feedstock chemicals—such as alcohols, acids, and halides—in permutation for construction single C(sp3)–C(sp3) bond. ability sort these two distinct radicals across commercially available alkenes in three-component manner would enable simultaneous bonds, greatly accelerating access drug-like chemical space. However, situ formation electrophilic nucleophilic presence unactivated is problematic, typically leading statistical recombination, hydrogen atom transfer, disproportionation, other deleterious pathways. Herein, we report use an alkene. This reaction involves three species, which are then differentiated size electronics, allowing regioselective desired dialkylated products. work accelerates pharmaceutically relevant C(sp3)-rich molecules defines novel mechanistic paradigm alkene dialkylation.

Language: Английский

Single catalyst double outer-sphere alkene cross-coupling

Published: Nov. 17, 2023

Cross-coupling catalysts typically react and unite functionally distinct partners via sequential inner-sphere elementary steps: coordination, migratory insertion, reductive elimination, etc. Here we report a single catalyst that cross-couples styrenes benzyl bromides iterative outer-sphere metal-ligand-carbon interactions. Each partner forms stabilized radical in-termediate yet hetero-coupled products predominate. The system is redox neutral thus avoids exogenous oxidant, resulting in simple scalable conditions. Numerous variations of alkene hydrobenzylation are made possible, including access to the privileged hetero-dibenzyl (1,2-diarylethane) motif challenging quaternary carbon variants.

Language: Английский