手性催化动力学拆分 2-锂代-N-Boc-哌啶的配体交换反应。
Dynamics of catalytic resolution of 2-lithio-N-Boc-piperidine by ligand exchange.
机构信息
Department of Chemistry and Biochemistry, University of Arkansas, Fayetteville, Arkansas 72701, USA.
出版信息
J Am Chem Soc. 2012 Oct 10;134(40):16845-55. doi: 10.1021/ja307796e. Epub 2012 Sep 25.
Abstract
The dynamics of the racemization and catalytic and stoichiometric dynamic resolution of 2-lithio-N-Boc-piperidine (7) have been investigated. The kinetic order in tetramethylethylenediamine (TMEDA) for both racemization and resolution of the title compound and the kinetic orders in two resolving ligands have been determined. The catalytic dynamic resolution is second order in TMEDA and 0.5 and 0.265 order in chiral ligands 8 and 10, respectively. The X-ray crystal structure of ligand 10 shows it to be an octamer. Dynamic NMR studies of the resolution process were carried out. Some of the requirements for a successful catalytic dynamic resolution by ligand exchange have been identified.
摘要
我们研究了 2-锂代-N-Boc-哌啶（7）的外消旋化和催化及计量动态拆分的动力学。确定了标题化合物外消旋化和拆分的四甲基乙二胺（TMEDA）动力学级数以及两种拆分配体的动力学级数。催化动态拆分在 TMEDA 中为二级，在手性配体 8 和 10 中分别为 0.5 和 0.265 级。配体 10 的 X 射线晶体结构表明其为八聚体。对拆分过程的动态 NMR 研究进行了开展。确定了通过配体交换实现成功催化动态拆分的一些要求。
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