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

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(4), С. 2351 - 2357

Опубликована: Янв. 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.

Язык: Английский

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Aminoalkylation of Alkenes Enabled by Triple Radical Sorting

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Янв. 9, 2025

The direct synthesis of C(sp3)-rich architectures is a driving force for innovation in synthetic organic chemistry. Such scaffolds impart beneficial properties onto drug molecules that correlate with greater clinical success. Consequently, there strong impetus to develop new methods by which access sp3-rich from commercial feedstocks, such as alkenes. Herein, we report three-component aminoalkylation reaction utilizes the principles triple radical sorting regioselectively add N-centered and C-centered radicals across This process relies upon photoredox catalysis transform alkyl bromides reductively activated precursors into high-energy species redox-neutral fashion. A broad scope coupling partners demonstrated, multiple applications, including facile syntheses pharmacophoric substituted N-heterocycles.

Язык: Английский

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Catalytic Asymmetric Radical–Polar Crossover Hydroalkoxylation

Journal of the American Chemical Society, Год журнала: 2019, Номер 141(44), С. 17527 - 17532

Опубликована: Окт. 23, 2019

Asymmetric intramolecular hydrofunctionalization of tertiary allylic alcohols is described. This metal hydride-mediated catalytic radical–polar crossover reaction delivers corresponding epoxides in good to high enantioselectivity and constitutes the first example asymmetric hydrogen atom transfer-initiated process. A series modified cobalt salen complexes has proven optimal for achieving efficiency induction. Experimental data suggest that cationic may be involved enantiodetermining step, where cation−π interactions catalyst contribute

Язык: Английский

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Radical‐Based Synthesis and Modification of Amino Acids

Angewandte Chemie International Edition, Год журнала: 2020, Номер 60(3), С. 1098 - 1115

Опубликована: Авг. 26, 2020

Abstract Amino acids (AAs) are key structural motifs with widespread applications in organic synthesis, biochemistry, and material sciences. Recently, the development of milder more versatile radical‐based procedures, use strategies relying on radical chemistry for synthesis modification AAs has gained increased attention, as they allow rapid access to libraries novel unnatural containing a wide range motifs. In this Minireview, we provide broad overview advancements made field during last decade, focusing methods de novo α‐, β‐, γ‐AAs, well selective derivatisation canonical non‐canonical α‐AAs.

Язык: Английский

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Nickel‐Catalyzed Regioselective Hydroalkylation and Hydroarylation of Alkenyl Boronic Esters

Angewandte Chemie International Edition, Год журнала: 2019, Номер 58(39), С. 13854 - 13859

Опубликована: Июль 8, 2019

Abstract Metal hydride catalyzed hydrocarbonation reactions of alkenes are an efficient approach to construct new carbon–carbon bonds from readily available alkenes. However, the regioselectivity remains challenging be controlled. In nickel (NiH) hydrocarbonation, linear selectivity is most often obtained because relative stability Ni–alkyl intermediate over its branched counterpart. Herein, we show that boronic pinacol ester (Bpin) group directs a Ni‐catalyzed occur at adjacent carbon center, resulting in formal branch selectivity. Both alkyl and aryl halides can used as electrophiles this providing access wide range secondary Bpin derivatives, which valuable building blocks synthetic chemistry. The utility method demonstrated by late‐stage functionalization natural products drug molecules, synthesis anticancer agent, iterative syntheses.

Язык: Английский

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