Batuecas Maria, Kong Richard Y, White Andrew J P, Crimmin Mark R
Department of Chemistry, MSRH, Imperial College London, 82 Wood Lane, Shepherds Bush, London, W12 0BZ, UK.
Angew Chem Int Ed Engl. 2022 May 9;61(20):e202202241. doi: 10.1002/anie.202202241. Epub 2022 Mar 16.
Selective reactions that combine H , CO and organic electrophiles (aldehyde, ketones, isocyanide) to form hydrogenated C and C carbon chains are reported. These reactions proceed by CO homologation mediated by [W(CO) ] 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 H and CO to make well-defined products with complete control over chain length and functionality.
报道了将氢、一氧化碳和有机亲电试剂（醛、酮、异腈）结合以形成氢化碳链和碳碳链的选择性反应。这些反应通过由[W(CO)₆]和一种一价铝还原剂介导的一氧化碳同系化反应进行，随后是链端的官能化和氢化反应。动力学（速率、动力学同位素效应）和密度泛函理论计算相结合，用于深入了解涉及金属卡宾中间体氢化的关键步骤。这些发现扩展了将氢和一氧化碳结合以制备具有对链长和官能团完全控制的明确产物的系统的极小范围。
