利用动力学拆分策略实现伯胺构型的纳摩尔级分配。

Nanomole-scale assignment of configuration for primary amines using a kinetic resolution strategy.

机构信息

Department of Chemistry, 1102 Natural Sciences II, University of California-Irvine, Irvine, California 92697, United States.

出版信息

J Am Chem Soc. 2012 Dec 19;134(50):20318-21. doi: 10.1021/ja310620c. Epub 2012 Dec 4.

DOI:10.1021/ja310620c

PMID:23210977

Abstract

The absolute configurations of primary amines were assigned using a kinetic resolution strategy with Mioskowski's enantioselective 1-(R,R) and 2-(S,S) acylating agents. A simple mnemonic was developed to determine the configuration. A pseudoenantiomeric pair of reagents, 1-(R,R) and 2-(S,S)-d(3), was prepared and used to assay primary amines on a micromolar scale. The ESI-MS readout of the resulting acetamide products reproduced the selectivity factors from kinetic experiments. The method can be used on mixtures of amines and was validated with amine samples as small as 50 nmol.

摘要

本文采用米奥斯基斯基（Mioskowski）具有对映选择性的 1-（R,R）和 2-（S,S）酰化试剂的动力学拆分策略，确定了伯胺的绝对构型。开发了一个简单的助记符来确定构型。制备了一对假对映体试剂 1-（R,R）和 2-（S,S）-d（3），并在微摩尔级上用于测定伯胺。所得乙酰胺产物的 ESI-MS 读出值重现了动力学实验的选择性因子。该方法可用于胺混合物，并通过 50nmol 小至 50nmol 的胺样品进行验证。