Engaging Alkenes in Metallaphotoredox: A Triple Catalytic, Radical Sorting Approach to Olefin-Alcohol Cross-Coupling DOI Creative Commons
Qinyan Cai, Iona M. McWhinnie, Nathan W. Dow

et al.

Published: Dec. 1, 2023

Metallaphotoredox cross-coupling is a well-established strategy for generating clinically privileged aliphatic scaffolds via open-shell reactivity. The introduction of new C(sp3)-coupling partners within this paradigm can provide entry to novel, medicinally-relevant chemical space. Alkenes are abundant, bench-stable and undergo facile C(sp3)-radical reactivity metal-hydride hydrogen atom transfer (MHAT), yet metallaphotoredox methodologies invoking remain underdeveloped. Importantly, the merger MHAT activation with catalysis could enable olefins feedstock radical only activated photocatalysis, such as alcohols. Herein, we report first C(sp3)–C(sp3) coupling MHAT-activated alkenes alcohols (i.e. deoxygenative hy-droalkylation) triple co-catalysis. Through synergistic Ir Mn Ni sorting pathways, branch-selective protocol pairs diverse methanol or primary alcohols, displays remarkable functional group tolerance, enables rapid construction complex frameworks.

Language: Английский

Alkene Hydrobenzylation by a Single Catalyst That Mediates Iterative Outer-Sphere Steps DOI

Lingran Kong,

Xu-cheng Gan, Vincent A. van der Puyl

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(4), P. 2351 - 2357

Published: Jan. 17, 2024

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 intermediate, yet heterocoupled products predominate. The system is redox-neutral and, thus, avoids exogenous oxidants, resulting in simple scalable conditions. Numerous variations of alkene hydrobenzylation are made possible, including access to the privileged heterodibenzyl (1,2-diarylethane) motif challenging quaternary carbon variants.

Language: Английский

Citations

19
Engaging Alkenes in Metallaphotoredox: A Triple Catalytic, Radical Sorting Approach to Olefin-Alcohol Cross-Coupling DOI Creative Commons
Qinyan Cai, Iona M. McWhinnie, Nathan W. Dow

et al.

Published: Dec. 1, 2023

Metallaphotoredox cross-coupling is a well-established strategy for generating clinically privileged aliphatic scaffolds via open-shell reactivity. The introduction of new C(sp3)-coupling partners within this paradigm can provide entry to novel, medicinally-relevant chemical space. Alkenes are abundant, bench-stable and undergo facile C(sp3)-radical reactivity metal-hydride hydrogen atom transfer (MHAT), yet metallaphotoredox methodologies invoking remain underdeveloped. Importantly, the merger MHAT activation with catalysis could enable olefins feedstock radical only activated photocatalysis, such as alcohols. Herein, we report first C(sp3)–C(sp3) coupling MHAT-activated alkenes alcohols (i.e. deoxygenative hy-droalkylation) triple co-catalysis. Through synergistic Ir Mn Ni sorting pathways, branch-selective protocol pairs diverse methanol or primary alcohols, displays remarkable functional group tolerance, enables rapid construction complex frameworks.

Language: Английский

Citations

2