Dataset Information

Directed Photochemically Mediated Nickel-Catalyzed (Hetero)arylation of Aliphatic C-H Bonds.

ABSTRACT: Site-selective functionalization of unactivated C(sp³)-H centers is challenging because of the ubiquity and strength of alkyl C-H bonds. Herein, we disclose a position-selective C(sp³)-C(sp²) cross-coupling reaction. This process engages C(sp³)-H bonds and aryl bromides, utilizing catalytic quantities of a photoredox-capable molecule and a nickel precatalyst. Using this technology, selective C-H functionalization arises owing to a 1,6-hydrogen atom transfer (HAT) process that is guided by a pendant alcohol-anchored sulfamate ester. These transformations proceed directly from N-H bonds, in contrast to previous directed, radical-mediated, C-H arylation processes, which have relied on prior oxidation of the reactive nitrogen center in reactions with nucleophilic arenes. Moreover, these conditions promote arylation at secondary centers in good yields with excellent selectivity.

SUBMITTER: Simons RT

PROVIDER: S-EPMC10423309 | biostudies-literature | 2023 Feb

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

Directed Photochemically Mediated Nickel-Catalyzed (Hetero)arylation of Aliphatic C-H Bonds.

Simons R Thomas RT Nandakumar Meganathan M Kwon Kitae K Ayer Suraj K SK Venneti Naresh M NM Roizen Jennifer L JL

Journal of the American Chemical Society 20230213

Site-selective functionalization of unactivated C(sp3)-H centers is challenging because of the ubiquity and strength of alkyl C-H bonds. Herein, we disclose a position-selective C(sp3)-C(sp2) cross-coupling reaction. This process engages C(sp3)-H bonds and aryl bromides, utilizing catalytic quantities of a photoredox-capable molecule and a nickel precatalyst. Using this technology, selective C-H functionalization arises owing to a 1,6-hydrogen atom tra ...[more]

PMID: 36780585

Similar Datasets

Project description:Despite the widespread success of transition-metal-catalysed cross-coupling methodologies, considerable limitations still exist in reactions at sp3-hybridized carbon atoms, with most approaches relying on prefunctionalized alkylmetal or bromide coupling partners1,2. Although the use of native functional groups (for example, carboxylic acids, alkenes and alcohols) has improved the overall efficiency of such transformations by expanding the range of potential feedstocks3-5, the direct functionalization of carbon-hydrogen (C-H) bonds-the most abundant moiety in organic molecules-represents a more ideal approach to molecular construction. In recent years, an impressive range of reactions that form C(sp3)-heteroatom bonds from strong C-H bonds has been reported6,7. Additionally, valuable technologies have been developed for the formation of carbon-carbon bonds from the corresponding C(sp3)-H bonds via substrate-directed transition-metal C-H insertion8, undirected C-H insertion by captodative rhodium carbenoid complexes9, or hydrogen atom transfer from weak, hydridic C-H bonds by electrophilic open-shell species10-14. Despite these advances, a mild and general platform for the coupling of strong, neutral C(sp3)-H bonds with aryl electrophiles has not been realized. Here we describe a protocol for the direct C(sp3) arylation of a diverse set of aliphatic, C-H bond-containing organic frameworks through the combination of light-driven, polyoxometalate-facilitated hydrogen atom transfer and nickel catalysis. This dual-catalytic manifold enables the generation of carbon-centred radicals from strong, neutral C-H bonds, which thereafter act as nucleophiles in nickel-mediated cross-coupling with aryl bromides to afford C(sp3)-C(sp2) cross-coupled products. This technology enables unprecedented, single-step access to a broad array of complex, medicinally relevant molecules directly from natural products and chemical feedstocks through functionalization at sites that are unreactive under traditional methods.

Dataset Information

Directed Photochemically Mediated Nickel-Catalyzed (Hetero)arylation of Aliphatic C-H Bonds.

Publications

Directed Photochemically Mediated Nickel-Catalyzed (Hetero)arylation of Aliphatic C-H Bonds.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets