通过计算分析支持的一种裂环莫雷烷衍生物的结构测定及形成机制

Structure Determination and Mechanism of Formation of a seco-Moreliane Derivative Supported by Computational Analysis.

作者信息

Chacón Morales Pablo A, Amaro-Luis Juan M, Kutateladze Andrei G

机构信息

Laboratory of Natural Products, Department of Chemistry, Faculty of Sciences, University of "Los Andes" , Mérida 5101, Venezuela.

Department of Chemistry and Biochemistry, University of Denver , Denver, Colorado 80208, United States.

出版信息

J Nat Prod. 2017 Apr 28;80(4):1210-1214. doi: 10.1021/acs.jnatprod.7b00041. Epub 2017 Mar 30.

DOI:10.1021/acs.jnatprod.7b00041

PMID:28358484

Abstract

Basic hydrolysis of a dichloromethane extract of Stevia lucida yielded (4R,5S,7R,9R,10R,11R)-7,9-dihydroxylongipin-2-en-1-one (1), which was oxidized and subjected to acidic conditions to generate the new seco-moreliane derivative 3. The structure of 3 was established based on NMR data interpretation and confirmed computationally. A plausible mechanism for the carbocationic rearrangement of the trione 2 to the seco-moreliane 3 was supported by DFT computations.

摘要

光叶甜菊二氯甲烷提取物的碱性水解产生了(4R,5S,7R,9R,10R,11R)-7,9-二羟基长叶松-2-烯-1-酮(1)，其经氧化并在酸性条件下生成了新的裂环莫雷烷衍生物3。通过核磁共振数据解析确定了3的结构，并经计算得到证实。密度泛函理论计算支持了三酮2向裂环莫雷烷3的碳正离子重排的合理机制。