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对映选择性铜-双(恶唑啉)催化环丙烷化反应中C1对称与C2对称配体

C1-symmetric versus C2-symmetric ligands in enantioselective copper-bis(oxazoline)-catalyzed cyclopropanation reactions.

作者信息

Fraile José M, García José I, Gissibl Anja, Mayoral José A, Pires Elísabet, Reiser Oliver, Roldán Marta, Villalba Isabel

机构信息

Departamento de Química Orgánica, ICMA, CSIC-Universidad de Zaragoza and IUCH, Universidad de Zaragoza, Pedro Cerbuna 12, 50009 Zaragoza, Spain.

出版信息

Chemistry. 2007;13(31):8830-9. doi: 10.1002/chem.200700681.

DOI:10.1002/chem.200700681
PMID:17674345
Abstract

A thorough experimental and theoretical study of the enantioselective cyclopropanation of alkenes catalyzed by chiral bis(oxazoline)- and azabis(oxazoline)-copper complexes, which comprise a new family of ligands that lack C2 symmetry, has been conducted. Surprisingly high enantioselectivities were observed with some of these ligands, which were rationalized on the basis of molecular modeling studies. The course of the asymmetric induction in connection with ligand symmetry and the implications for supported enantioselective catalysts are discussed.

摘要

对手性双(恶唑啉)和氮杂双(恶唑啉)-铜配合物催化烯烃对映选择性环丙烷化反应进行了全面的实验和理论研究,这些配合物包含一类缺乏C2对称性的新型配体。使用其中一些配体时观察到了出奇高的对映选择性,并根据分子模型研究对其进行了合理化解释。讨论了与配体对称性相关的不对称诱导过程以及对负载型对映选择性催化剂的影响。

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