文章摘要
张雷.一种合成α-鼠胆酸的新方法[J].精细化工,2019,36(9):
一种合成α-鼠胆酸的新方法
A new method for the synthesis of a-muricholic acid
投稿时间:2019-05-16  修订日期:2019-06-29
DOI:
中文关键词: 猪去氧胆酸  a-鼠胆酸  选择性氧化  羟基化  水解
英文关键词: hyodeoxycholic acid  a-muricholic acid  selective oxidation  hydroxylation  hydrolysis
基金项目:
作者单位E-mail
张雷 华南理工大学生物科学与工程学院 lzhangce@scut.edu.cn 
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中文摘要:
      猪去氧胆酸为原料,经酯化、C-6位选择性氧化、C-7位羟基化、C-6位羰基还原和水解等步骤合成α-鼠胆酸,结构经1H-NMR、13C-NMR、HRMS确认,反应总收率达到28.9±0.3%。考察了催化剂对中间体Ⅱ收率的影响和工艺稳定性;探索了不同氧化剂对中间体Ⅱ中C-3和C-6位羟基氧化的选择性及收率,筛选到可高效选择性氧化C-6位羟基的氧化剂2-碘酰基苯甲酸(IBX),及其与中间体Ⅱ的物料比对中间体Ⅲ收率的影响及工艺稳定性。研究结果表明,1) 浓盐酸作为催化剂,中间体Ⅱ的收率达到99.0%;2)IBX可以选择性氧化中间体Ⅱ中C-6位羟基,且当n(中间体Ⅱ): n(IBX)=1: 1.20时,中间体Ⅲ的收率达到82.3%;3) 获得了中间体Ⅲ的X-射线单晶结构,确定了其绝对构型。
英文摘要:
      α-Muricholic acid was synthesized from hyodeoxycholic acid via esterification, selective oxidation, hy-droxylation of C-7 methylene, carbonyl reduction at C-6 and hydrolysis reactions. The resulting product was finally confirmed by 1H-NMR, 13C-NMR and HRMS. The overall yield from hyodeoxycholic acid was calculated to be 28.9±0.3%. The effect of catalysts on the yield of intermediateⅡand the process stability of the esterification reaction was investigated. The oxidants on the selective oxidation of C-3 or C-6 hy-droxyl group in intermediate Ⅱ were screened, and 2-iodobenzoic acid (IBX) was approved to be good candidate in selective oxidation of the C-6 hydroxyl group in intermediate Ⅱ. The effects of the molecu-lar ratio of Ⅱ to IBX on the yield of intermediate Ⅲ and the process stability under the conditions were explored, and the results were as follow: 1) the yield of intermediate Ⅱ was 99.0% by using concentrated HCl as the catalyst; 2) IBX could selectively oxidize hydroxyl group at C-6 of intermediate Ⅱ and the yield of the intermediate Ⅲ was 82.3% when the ratio of n (Ⅱ): n (IBX) was 1: 1.20; 3) the single crystal structure of intermediate Ⅲ was determined, and its absolute configuration was as expected.
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