赤藓糖型-1-萘基-1-(2-哌啶基)甲醇：合成、拆分、核磁共振相对构型及振动圆二色光谱绝对构型

erythro-1-Naphthyl-1-(2-piperidyl)methanol: synthesis, resolution, NMR relative configuration, and VCD absolute configuration.

作者信息

Solladié-Cavallo A, Marsol C, Yaakoub M, Azyat K, Klein A, Roje M, Suteu C, Freedman T B, Cao X, Nafie L A

机构信息

Laboratoire de Stéréochimie Organométallique, ECPM/Université Louis Pasteur, 67087 Strasbourg, France.

出版信息

J Org Chem. 2003 Sep 19;68(19):7308-15. doi: 10.1021/jo0345502.

DOI:10.1021/jo0345502

PMID:12968880

Abstract

The erythro isomer of 1-naphthyl-1-(2-piperidyl)methanol 4, an efficient chiral modifier for asymmetric heterogeneous hydrogenation, was obtained as the major isomer (95%) in two steps while the threo isomer can be obtained as the major isomer (67%) in three steps. erythro-4 and threo-4 were resolved on a CHIRALCEL OD-RH column. It has been shown by VCD that the diastereomer determined as the erythro by NMR was indeed the erythro and that the first eluted (-)-enantiomer on CHIRALCEL OD-R or -RH columns has the (1R,2S) configuration. The VCD studies identify the presence of at least five conformers in CDCl(3) solution. Moreover, this (-)-(1R,2S) absolute configuration found by VCD is consistent with the expected stereo-outcome of catalytic hydrogenation of pyruvate into lactate, which supported the (+)-(1S,2R) assignment.

摘要

1-萘基-1-(2-哌啶基)甲醇4的赤藓糖异构体是一种用于不对称多相氢化的高效手性修饰剂，分两步得到主要异构体(95%)，而苏阿糖异构体可分三步得到主要异构体(67%)。赤藓糖-4和苏阿糖-4在CHIRALCEL OD-RH柱上进行拆分。VCD已表明，通过核磁共振确定为赤藓糖的非对映异构体确实是赤藓糖，并且在CHIRALCEL OD-R或-RH柱上第一个洗脱的(-)-对映体具有(1R,2S)构型。VCD研究确定在CDCl₃溶液中至少存在五种构象。此外，通过VCD发现的这种(-)-(1R,2S)绝对构型与丙酮酸催化氢化成乳酸的预期立体结果一致，这支持了(+)-(1S,2R)的归属。