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Diversification of aliphatic C-H bonds in small molecules and polyolefins through radical chain transfer.

ABSTRACT: The ability to selectively introduce diverse functionality onto hydrocarbons is of substantial value in the synthesis of both small molecules and polymers. Herein, we report an approach to aliphatic carbon-hydrogen bond diversification using radical chain transfer featuring an easily prepared O-alkenylhydroxamate reagent, which upon mild heating facilitates a range of challenging or previously undeveloped aliphatic carbon-hydrogen bond functionalizations of small molecules and polyolefins. This broad reaction platform enabled the functionalization of postconsumer polyolefins in infrastructure used to process plastic waste. Furthermore, the chemoselective placement of ionic functionality onto a branched polyolefin using carbon-hydrogen bond functionalization upcycled the material from a thermoplastic into a tough elastomer with the tensile properties of high-value polyolefin ionomers.

SUBMITTER: Fazekas TJ

PROVIDER: S-EPMC8889563 | biostudies-literature | 2022 Feb

REPOSITORIES: biostudies-literature

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Diversification of aliphatic C-H bonds in small molecules and polyolefins through radical chain transfer.

Fazekas Timothy J TJ Alty Jill W JW Neidhart Eliza K EK Miller Austin S AS Leibfarth Frank A FA Alexanian Erik J EJ

Science (New York, N.Y.) 20220203 6580

The ability to selectively introduce diverse functionality onto hydrocarbons is of substantial value in the synthesis of both small molecules and polymers. Herein, we report an approach to aliphatic carbon-hydrogen bond diversification using radical chain transfer featuring an easily prepared <i>O</i>-alkenylhydroxamate reagent, which upon mild heating facilitates a range of challenging or previously undeveloped aliphatic carbon-hydrogen bond functionalizations of small molecules and polyolefins ...[more]

PMID: 35113718

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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

Diversification of aliphatic C-H bonds in small molecules and polyolefins through radical chain transfer.

Publications

Diversification of aliphatic C-H bonds in small molecules and polyolefins through radical chain transfer.

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