Carbon Dioxide Activation Center (CADIAC), Department of Chemistry and the Interdisciplinary Nanoscience Center (iNANO), Aarhus University, Gustav Wieds Vej 14, 8000, Aarhus C, Denmark.
Isotope Chemistry, Early Chemical Development, Pharmaceutical Sciences, R&D, AstraZeneca Pharmaceuticals, 43183, Gothenberg, Sweden.
Angew Chem Int Ed Engl. 2020 May 18;59(21):8099-8103. doi: 10.1002/anie.201916391. Epub 2020 Mar 2.
An extensive range of functionalized aliphatic ketones with good functional-group tolerance has been prepared by a Ni -promoted coupling of either primary or secondary alkyl iodides with NN pincer Ni -acyl complexes. The latter were easily accessed from the corresponding Ni -alkyl complexes with stoichiometric CO. This Ni-mediated carbonylative coupling is adaptable to late-stage carbon isotope labeling, as illustrated by the preparation of isotopically labelled pharmaceuticals. Preliminary investigations suggest the intermediacy of carbon-centered radicals.
通过 Ni 促进的伯烷基碘或仲烷基碘与 NN 钳形 Ni-酰基配合物的偶联反应，制备了具有良好官能团耐受性的各种功能化脂肪族酮。后者可以通过与等摩尔 CO 的相应 Ni-烷基配合物很容易获得。这种 Ni 介导的羰基偶联反应适用于后期的碳同位素标记，如通过制备同位素标记的药物所说明的。初步研究表明碳中心自由基的中间性。
