[2.2.2]-酰基硝酮环加成物的区域选择性铜催化烷基化反应：格氏试剂卤化物的显著影响。

Regioselective copper-catalyzed alkylation of [2.2.2]-acylnitroso cycloadducts: remarkable effect of the halide of Grignard reagents.

机构信息

Dipartimento di Scienze Farmaceutiche, Sede di Chimica Bioorganica e Biofarmacia, Universita di Pisa, Via Bonanno 33, 56126 Pisa, Italy.

出版信息

Org Lett. 2010 Apr 16;12(8):1828-30. doi: 10.1021/ol100454c.

DOI:10.1021/ol100454c

PMID:20232855

Abstract

Ring opening with organometallic reagents of [2.2.2]-acylnitroso cycloadducts, including an enantioselective kinetic resolution of these compounds, has been accomplished for the first time. By the careful choice of reaction conditions, it was possible to obtain new cyclohexenyl hydroxamic acids with complete anti-stereoselectivity and a nice regioalternating control. A remarkable effect of the halogen of the Grignard reagent was observed during ring opening.

摘要

首次实现了[2.2.2]-酰基硝酮环加成物的有机金属试剂开环反应，包括这些化合物的对映选择性动力学拆分。通过仔细选择反应条件，有可能获得具有完全反立体选择性和良好区域交替控制的新环己烯基羟肟酸。在开环过程中观察到格氏试剂卤素的显著影响。