苹果酸——天然产物对映选择性全合成和合成方法学中多用途的手性合成砌块  

Malic acid——A Versatile Chiral Building Block in the Enantioselective Total Synthesis of Natural Products and in Synthetic Methodologies

作　　者：罗世鹏 黄培强[2,3] Shipeng Luo;Peiqiang Huang(School of Chemistry and Environmental Engineering,Jiangsu University of Technology,Changzhou 213001,China;iChEM(Collaborative Innovation Center of Chemistry for Energy Materials),College of Chemistry and Chemical Engineering,Xiamen University,Xiamen 361005,China;Department of Chemistry,Fujian Provincial Key Laboratory of Chemical Biology,Xiamen 361005,China)

机构地区：[1]江苏理工学院化学与环境工程学院,常州213001 [2]能源材料化学协同创新中心厦门大学化学化工学院化学系,厦门361005 [3]福建省化学生物学重点实验室,厦门361005

出　　处：《化学进展》2020年第11期1846-1868,共23页Progress in Chemistry

基　　金：国家重点研发计划(No.2017YFA0207302);国家自然科学基金项目(No.21672176,21931010);教育部长江学者和创新团队发展计划资助。

摘　　要：合成砌块策略是天然产物生源合成的基本策略之一。对映纯天然手性合成砌块,由于价廉、易得,在天然产物的对映选择性全合成中获得广泛应用。这一策略,兴起于四十年前,至今仍是复杂分子对映选择性全合成的重要工具。L-苹果酸是一种价廉易得的天然手性源,D-苹果酸虽然价格稍贵,也是一种商品化试剂。苹果酸所包含的四个碳原子均可被转化或官能化,因而被广泛应用于各类天然产物的对映选择性全合成。本文综述了L-和D-苹果酸在有机合成中的应用进展:归纳总结了从苹果酸衍生的多种C_4手性合成砌块,重点评述了近年来这些合成砌块在复杂天然产物全合成中的应用,结合作者实验室的工作介绍基于苹果酸的新型合成方法学研究进展,并对基于苹果酸的合成方法学的发展进行了展望。Building block-approach is one of the basic strategies used by nature in biogenetic synthesis.Naturally occurring L-α-amino acids,L-α-hydroxy acids,D-mono-sugars,and terpenes,being cheap and easily available in enantiopure forms,have found widespread applications enantioselective synthesis as chiral building blocks.LMalic acid,an L-α-hydroxy diacid,is a readily available and cheap natural chiron,D-malic acid is also commercially available although it is more expensive.With all of the four carbon atoms transformable or functionalizable,malic acid serves as a versatile C4 building block in organic synthesis for enantioselective synthesis.In this review,the progress in the applications of malic acid in organic synthesis is summarized.Firstly,the transformations of malic acid into a variety of advanced chiral C4 building blocks are compiled.Secondly,selected examples on the applications of these versatile intermediates in the total synthesis of complex natural products in recent years are presented.Besides,the developments of malic acid-based new synthetic methodologies including the contribution from one of the authors’laboratory are highlighted.An outlook for future development of malic acid-based synthetic strategy is provided.

关 键 词：L-苹果酸 手性合成砌块 天然产物 全合成 合成方法 对映选择性合成 仿生策略 

分 类 号：O641.4[理学—物理化学] O635[理学—化学]