具有平面和中心手性的结构多样的第二代[2.2]对环芳烷酮亚胺：合成、结构测定及不对称催化评估

Structurally diverse second-generation [2.2]paracyclophane ketimines with planar and central chirality: syntheses, structural determination, and evaluation for asymmetric catalysis.

作者信息

Lauterwasser Frank, Nieger Martin, Mansikkamäki Heidi, Nättinen Kalle, Bräse Stefan

机构信息

Institut für Organische Chemie, Universität Karlsruhe TH, Fritz-Haber-Weg 6, 76131 Karlsruhe, Germany.

出版信息

Chemistry. 2005 Jul 18;11(15):4509-25. doi: 10.1002/chem.200500146.

DOI:10.1002/chem.200500146

PMID:15880686

Abstract

A set of 20 novel [2.2]paracyclophane ketimines with planar and central chirality has been synthesized from enantiomerically pure and racemic 5-acyl-4-hydroxy[2.2]paracyclophane and alpha-branched chiral amines. Their X-ray structures were determined to elucidate the three-dimensional structures and the absolute configuration. The ketimines were used as catalysts in the asymmetric 1,2-addition reactions of diethylzinc with substituted benzaldehydes to furnish chiral alcohols in up to 95 % ee.

摘要

由对映体纯的外消旋5-酰基-4-羟基[2.2]对环芳烷和α-支链手性胺合成了一组20种具有平面和中心手性的新型[2.2]对环芳烷酮亚胺。测定了它们的X射线结构以阐明三维结构和绝对构型。这些酮亚胺被用作二乙基锌与取代苯甲醛不对称1,2-加成反应的催化剂，以高达95%的对映体过量提供手性醇。