von Köller Heinrich F, Jones Peter G, Werz Daniel B
Albert-Ludwigs-Universität Freiburg, Institute of Organic Chemistry, Albertstraße 21, 79104, Freiburg im Breisgau, Germany.
Technische Universität Braunschweig, Institute of Inorganic and Analytical Chemistry, Hagenring 30, 38106, Braunschweig, Germany.
Chemistry. 2023 Apr 6;29(20):e202203986. doi: 10.1002/chem.202203986. Epub 2023 Feb 28.
A 1,3-carbocarbonation of 2-substituted cyclopropane 1,1-dicarboxylates introduces various saturated or unsaturated carbon residues at the 1- and 3- position of the former three-membered ring. Under copper catalysis, ring-opening attack with a Grignard reagent proceeded smoothly; the intermediate was converted to the final product by reaction with appropriate carbon-based electrophiles under basic conditions. As nucleophiles, Grignard reagents derived from sp -, sp -, and sp-hybridized carbon residues were successfully employed, whereas various aliphatic bromides and EBX derivatives (for sp moieties) served as electrophiles.
2-取代环丙烷-1,1-二羧酸酯的1,3-碳羧化反应在前述三元环的1-位和3-位引入了各种饱和或不饱和碳残基。在铜催化下，格氏试剂的开环进攻顺利进行；中间体在碱性条件下与合适的碳基亲电试剂反应转化为最终产物。作为亲核试剂，成功使用了源自sp-、sp-和sp-杂化碳残基的格氏试剂，而各种脂肪族溴化物和EBX衍生物（用于sp部分）用作亲电试剂。
