Department of Chemistry , University of Kansas , 1567 Irving Hill Road , Lawrence , Kansas 66045 , United States.
Department of Chemistry , North Caucasus Federal University , 1a Pushkin Street , Stavropol 355009 , Russian Federation.
J Org Chem. 2018 Aug 3;83(15):8426-8448. doi: 10.1021/acs.joc.8b01063. Epub 2018 Jul 6.
Copper-catalyzed, directed addition of Grignard reagents across the strained C═C bond of cyclopropene-3-carboxamides was developed. It was demonstrated that the amide functionality serves as an ultimate directing group allowing for highly efficient control of diastereoselectivity of addition including stereoselectivity of electrophilic trapping with prochiral aldehydes. Also, regioselectivity of carbomagnesiation of cyclopropenes with a monosubstituted double bond is investigated. It was shown that in many cases this selectivity is controlled by steric factors and allows for preparation of products with a "reversed" regiochemistry.
发展了铜催化的、导向的格氏试剂对环丙烯-3-羧酰胺的张力 C═C 键的加成。结果表明，酰胺官能团可作为最终的导向基团，允许对加成的非对映选择性进行高度有效的控制，包括与前手性醛的立体选择性的亲电捕获。此外，还研究了单取代双键的环丙烷的碳镁化的区域选择性。结果表明，在许多情况下，这种选择性受立体因素控制，并允许制备具有“反向”区域化学的产物。
