Laboratório de Química Bioorgânica, Instituto de Pesquisas de Produtos Naturais , Universidade Federal do Rio de Janeiro, Ilha do Fundão, CCS , Bloco H-Sala H27 , 21941-902 Rio de Janeiro , RJ , Brazil.
Departamento de Química Orgánica I, Facultad de Química , Universidad del País Vasco/Euskal Herriko Unibertsitatea UPV/EHU , P. K. 1072 , E-20018 San Sebastián , Spain.
J Org Chem. 2019 Sep 6;84(17):10593-10605. doi: 10.1021/acs.joc.9b00267. Epub 2019 Aug 9.
Catalytic enantioselective 1,3-dipolar cycloaddition between imino esters and electrophilic alkenes, employing chiral metal complexes derived from copper(I) and silver(I) salts and ()-DM- or ()-DTBM-Segphos as ligands produces diastereodivergently exo- or endo-cycloadducts, respectively. The effect of the functional group of the dipolarophile and the fine tuning of the catalyst plays an important role in promoting reverse diastereoselectivities. The origins of experimentally observed enantioselectivity and diastereoselectivity data, as well as the origin of the observed switched endo/exo ratios, are also explained by means of density functional theory calculations.
手性金属配合物催化的亚胺酯与亲电烯烃的催化对映选择性 1,3-偶极环加成反应，以铜 (I) 和银 (I) 盐和 ()-DM-或 ()-DTBM-Segphos 作为配体衍生的手性金属配合物，分别产生非对映选择性地外消旋或内消旋环加成产物。二极性亲电试剂的官能团的影响和催化剂的精细调节在促进反式非对映选择性中起着重要作用。实验观察到的对映选择性和非对映选择性数据的起源，以及观察到的反式内/外比的起源，也可以通过密度泛函理论计算来解释。
