Ni-Electrocatalytic Decarboxylative Arylation to Access Quaternary Centers

Опубликована: Июль 25, 2023

There is an urgent need, particularly in the field of drug discovery, for general methods that will enable direct coupling tertiary alkyl fragments to (hetero)aryl halides. This early disclosure serves this purpose by informing community a uniquely powerful and simple set conditions achieving transformation with unparalleled generality chemoselectivity.

Язык: Английский

A Paradigm Shift in Catalysis: Electro- and Photomediated Nickel-Catalyzed Cross-Coupling Reactions

Опубликована: Авг. 3, 2023

Transition-metal cata-lyzed cross-coupling reactions are fundamental in organic chemistry, facilitating strategic bond formations for accessing natural products, mate-rials, agrochemicals, and pharmaceuticals. Redox chemistry enables access to elusive mechanisms through single-electron processes as an alternative classical two-electron strategies, which predominated by palladium catalysis. The hallmark of this redox platform is the systematic modulation transition-metal oxidation states a photoredox catalyst or at heterogeneous electrode sur-face. Electrocatalysis photocatalysis enhance transition metal catalysis’ capacity formation electron- energy-transfer processes. Cross-coupling conditions promoted electrocatalysis mild proceeds with exceptionally high chemoselectivity wide functional group tolerance. interfacing abundant first-row catalysis has brought about paradigm shift technology. In particular, merger Ni electro- photochemistry ushered new era carbon-carbon carbon-heteroatom cross-couplings. We have developed enabling photo- electrochemical methods throughout our research experience industry (BMS, AstraZeneca), academia (Professor Baran, Scripps Research), cross-disciplinary collaborative environments. Account, we will outline recent progress from past present labs electrochemically mediated Ni-catalyzed By highlighting these methodologies, also compare mechanistic features both electro– photochemical strategies forging C(sp2)–C(sp3), C(sp3)–C(sp3), C–O, C–N, C–S bonds. each case study where did not specifically develop approaches, highlight related work others education. Through side-by-side comparisons, hope demystify subtle differences between two complementary tools enact control over Finally, building off collective ourselves rest community, propose user guide electrochemically-driven aid practitioner rapidly applying such their synthetic designs.

Язык: Английский

Unlocking Tertiary Acids for Metallaphotoredox C(sp2)-C(sp3) Decarboxylative Cross-Couplings

Опубликована: Июнь 19, 2023

Dual nickel photoredox catalysis conditions have been developed for the decarboxylative cross-coupling of aryl halides and carboxylic acids containing fully substituted alpha carbons, a valuable but challenging substrate class C(sp2)–C(sp3) bond-forming reactions. High-throughput experimentation identified Ni(TMHD)2 as optimal precatalyst this reaction in contrast to nickel-bipyridyl complexes typically employed couplings, which predominantly furnished undesired C–O products. Computational work provides insight into potential mechanistic underpinnings C–C vs. selectivity nickel-diketonate complex.

Язык: Английский