How to Achieve Hydrogenation/Hydrofunctionalization via Metal Hydride Complexes DOI

Ju Peng,

Ruopeng Bai, Yu Lan

и другие.

Accounts of Chemical Research, Год журнала: 2025, Номер unknown

Опубликована: Апрель 20, 2025

ConspectusMetal hydride (M-H) complexes have garnered widespread attention in the synthesis of fine chemicals, materials, agrochemicals, and pharmaceuticals owing to remarkable reactivity M-H bonds. Specifically, are active intermediates that catalyze hydrogen-transfer reactions, leading efficient hydrogenation hydrofunctionalization C═C/C═X (X = O or N) bonds unsaturated organic substrates for formation new carbon-hydrogen, carbon-carbon, carbon-heteroatom bonds.Our research group has long studied transformation mechanisms, with significant advancements over past decade. For this Account, we drawn on our extensive expertise investigate mechanisms governing numerous transformation-driven including inert C═X compounds, bonds, dehydrogenative coupling, C-H functionalizations. On basis these mechanistic investigations, developed a series representative models, which offer robust theoretical guidance modulating selectivity hydrofunctionalization.Our Account begins structures properties complexes, lead homolytic heterolytic cleavage reactions different conditions, showcasing versatility metal reactivity. Based principles, three modes discussed. First, transfer low-oxidation-state is chiefly engaged because hydrogen atom attached high electron density strongly nucleophilic. In case, serves as from center electropositive substrate through following pathways: (a) insertion an bond into bond; (b) direct electrophilic site (c) σ-bond metathesis; (d) oxidative migration. Reductive elimination might also occur when oxidation state increases becomes electron-deficient. This usually regenerates catalytic species while producing C/X'-H Notably, (MHAT) advanced approach radical-type hydrofunctionalizations. MHAT induced by one-electron redox process enabled paramagnetic low dissociation energy (BDE) values. Two possible types (i.e., spontaneous passive), regioselectivities, proposed. article provides detailed account strategies related transformations, thus offering valuable rational design novel reaction systems.

Язык: Английский

How to Achieve Hydrogenation/Hydrofunctionalization via Metal Hydride Complexes DOI

Ju Peng,

Ruopeng Bai, Yu Lan

и другие.

Accounts of Chemical Research, Год журнала: 2025, Номер unknown

Опубликована: Апрель 20, 2025

ConspectusMetal hydride (M-H) complexes have garnered widespread attention in the synthesis of fine chemicals, materials, agrochemicals, and pharmaceuticals owing to remarkable reactivity M-H bonds. Specifically, are active intermediates that catalyze hydrogen-transfer reactions, leading efficient hydrogenation hydrofunctionalization C═C/C═X (X = O or N) bonds unsaturated organic substrates for formation new carbon-hydrogen, carbon-carbon, carbon-heteroatom bonds.Our research group has long studied transformation mechanisms, with significant advancements over past decade. For this Account, we drawn on our extensive expertise investigate mechanisms governing numerous transformation-driven including inert C═X compounds, bonds, dehydrogenative coupling, C-H functionalizations. On basis these mechanistic investigations, developed a series representative models, which offer robust theoretical guidance modulating selectivity hydrofunctionalization.Our Account begins structures properties complexes, lead homolytic heterolytic cleavage reactions different conditions, showcasing versatility metal reactivity. Based principles, three modes discussed. First, transfer low-oxidation-state is chiefly engaged because hydrogen atom attached high electron density strongly nucleophilic. In case, serves as from center electropositive substrate through following pathways: (a) insertion an bond into bond; (b) direct electrophilic site (c) σ-bond metathesis; (d) oxidative migration. Reductive elimination might also occur when oxidation state increases becomes electron-deficient. This usually regenerates catalytic species while producing C/X'-H Notably, (MHAT) advanced approach radical-type hydrofunctionalizations. MHAT induced by one-electron redox process enabled paramagnetic low dissociation energy (BDE) values. Two possible types (i.e., spontaneous passive), regioselectivities, proposed. article provides detailed account strategies related transformations, thus offering valuable rational design novel reaction systems.

Язык: Английский

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