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合成中间体的半缩酮和羟基酮互变异构体的分离，每种异构体均能生成18-羟基皮质醇- 。

Isolation of Hemiketal and Hydroxy Ketone Tautomers of Synthetic Intermediates Each Affording 18-Hydroxycortisol-.

作者信息

Lewin Anita H, Hayes James P, Zhong Desong, Zhang Dehui, Kormos Chad M, Mascarella S Wayne, Seltzman Herbert H

机构信息

Center for Drug Discovery, Research Triangle Institute, Research Triangle Park, North Carolina 27709-2194, United States.

出版信息

ACS Omega. 2023 Jul 26;8(31):28185-28195. doi: 10.1021/acsomega.3c01648. eCollection 2023 Aug 8.

DOI:10.1021/acsomega.3c01648
PMID:37576635
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC10413467/
Abstract

During the synthesis of deuterated 18-hydroxycortisol, two of the synthetic intermediates have been found to exist in tautomeric forms as the acyclic 18-hydroxy 20-ketone and the cyclic 18,20-hemiketal corresponding to the previously identified less polar (L) and more polar (M) forms of C-18 hydroxylated steroids, respectively. Specifically, -chloranil oxidation of 18-hydroxycortisol-17,21-acetonide afforded two isomers of the 6,7-dehydro analogue; separate catalytic reduction of each isomer under deuterium gave a single isomer of acetonide-protected 18-hydroxycortisol- for each, with the more polar isomer giving a more polar product and the less polar isomer giving a less polar product. The more polar product (corresponding to M) was characterized as 18,20-hemiketal; 18-hydroxycortisol-17,21-acetonide-18,20-hemiketal-: in the deuterochloroform solution, it was found to slowly convert to a substance consistent with the hydroxy ketone structure with features resembling those of the isolated less polar isomer (corresponding to L). Deacetonidization of each gave 18-hydroxycortisol as a single product, which was characterized as the 18,20-hemiketal. The issues associated with the existence of 18-hydroxysteroids as hydroxy ketones and hemiketals, both in solution and as isolable solids, are discussed.

摘要

在氘代18-羟皮质醇的合成过程中，已发现两种合成中间体以互变异构形式存在，即分别对应于先前鉴定的C-18羟基化甾体的极性较小（L）和极性较大（M）形式的无环18-羟基-20-酮和环状18,20-半缩酮。具体而言，18-羟皮质醇-17,21-丙酮化物的四氯苯醌氧化得到6,7-脱氢类似物的两种异构体；在氘气下对每种异构体进行单独的催化还原，每种都得到丙酮化物保护的18-羟皮质醇的单一异构体，极性较大的异构体得到极性较大的产物，极性较小的异构体得到极性较小的产物。极性较大的产物（对应于M）被表征为18,20-半缩酮；18-羟皮质醇-17,21-丙酮化物-18,20-半缩酮：在氘代氯仿溶液中，发现它会缓慢转化为一种与羟基酮结构一致的物质，其特征类似于分离出的极性较小的异构体（对应于L）。每种物质的脱丙酮化反应都得到单一产物18-羟皮质醇，其被表征为18,20-半缩酮。本文讨论了18-羟基甾体在溶液中和作为可分离固体时以羟基酮和半缩酮形式存在所涉及的问题。

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