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Functionalization and Hydrogenation of Carbon Chains Derived from CO.

ABSTRACT: Selective reactions that combine H₂ , CO and organic electrophiles (aldehyde, ketones, isocyanide) to form hydrogenated C₃ and C₄ carbon chains are reported. These reactions proceed by CO homologation mediated by [W(CO)₆ ] and an aluminum(I) reductant, followed by functionalization and hydrogenation of the chain ends. A combination of kinetics (rates, KIEs) and DFT calculations has been used to gain insight into a key step which involves hydrogenation of a metallocarbene intermediate. These findings expand the extremely small scope of systems that combine H₂ and CO to make well-defined products with complete control over chain length and functionality.

SUBMITTER: Batuecas M

PROVIDER: S-EPMC9311202 | biostudies-literature | 2022 May

REPOSITORIES: biostudies-literature

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Functionalization and Hydrogenation of Carbon Chains Derived from CO.

Batuecas Maria M Kong Richard Y RY White Andrew J P AJP Crimmin Mark R MR

Angewandte Chemie (International ed. in English) 20220316 20

Selective reactions that combine H2 , CO and organic electrophiles (aldehyde, ketones, isocyanide) to form hydrogenated C3 and C4 carbon chains are reported. These reactions proceed by CO homologation mediated by [W(CO)6 ] and an aluminum(I) reductant, followed by functionalization and hydrogenation of the chain ends. A combination of kinetics (rates, KIEs) and DFT calculations has been used to gain insight into a key step which involves hydrogenation ...[more]

PMID: 35225403

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