甲亚胺叶立德与α,β-不饱和酮的催化不对称1,3-偶极环加成反应

Catalytic asymmetric 1,3-dipolar cycloaddition of azomethine ylides with alpha,beta-unsaturated ketones.

作者信息

Hernández-Toribio Jorge, Gómez Arrayás Ramón, Martín-Matute Belén, Carretero Juan C

机构信息

Departamento de Química Orgánica, Facultad de Ciencias, Universidad Autónoma de Madrid, Cantoblanco, 28049 Madrid, Spain.

出版信息

Org Lett. 2009 Jan 15;11(2):393-6. doi: 10.1021/ol802664m.

DOI:10.1021/ol802664m

PMID:19093844

Abstract

Alpha,beta-unsaturated ketones are no longer the missing dipolarophiles in catalytic asymmetric 1,3-dipolar cycloaddition of azomethine ylides. In the presence of Cu(I)-Fesulphos complexes as catalysts (5 mol %), these substrates combine high reactivity, wide substitution tolerance, moderate to good endo/exo selectivities, and high enantiocontrol. The endo/exo-diastereoselectivity of the reaction is strongly dependent on the cis or trans nature of the enone moiety.

摘要

在甲亚胺叶立德的催化不对称1,3-偶极环加成反应中，α,β-不饱和酮不再是缺失的亲偶极体。在Cu(I)-Fesulphos配合物作为催化剂（5 mol%）存在的情况下，这些底物具有高反应活性、广泛的取代耐受性、中等至良好的内型/外型选择性以及高对映体控制。该反应的内型/外型非对映选择性强烈依赖于烯酮部分的顺式或反式性质。