Functionalization and Hydrogenation of Carbon Chains Derived from CO

Maria Batuecas; Richard Y Kong; Andrew J P White; Mark R Crimmin

doi:10.1002/anie.202202241

Functionalization and Hydrogenation of Carbon Chains Derived from CO

Angew Chem Int Ed Engl. 2022 May 9;61(20):e202202241. doi: 10.1002/anie.202202241. Epub 2022 Mar 16.

Authors

Maria Batuecas¹, Richard Y Kong¹, Andrew J P White¹, Mark R Crimmin¹

Affiliation

¹ Department of Chemistry, MSRH, Imperial College London, 82 Wood Lane, Shepherds Bush, London, W12 0BZ, UK.

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.

Keywords: CO; Fischer-Tropsch; Homologation; Metallocarbenes; Reaction Mechanisms.

Abstract

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