天然产物的仿生全合成:回顾与展望
黄培强

(厦门大学化学化工学院化学系,福建省化学生物学重点实验室,福建 厦门 361005)

仿生合成; 概念; 全合成; 合成策略; 天然产物; 虎皮楠生物碱

Biomimetic total synthesis of natural products:retrospect and prospect
HUANG Peiqiang

(Fujian Provincial Key Laboratory of Chemical Biology,Department of Chemistry,College of Chemistry and Chemical Engineering,Xiamen University,Xiamen 361005,China)

DOI: 10.6043/j.issn.0438-0479.202009016

备注

以仿生合成的3个经典,即Robinson的托品酮一步仿生合成、Heathcock的虎皮楠生物碱外消旋仿生全合成和Husson的白刺生物碱(+)-isonitramine的4步仿生不对称全合成,大体勾勒仿生合成的发展脉络及其对有机化学学科的促进作用,同时指出存在的问题; 在此基础上提出对拓展仿生合成理念的思考,即把Breslow原来的定义拓展到对自然界生物合成策略的模仿.进而以本课题组实现的(-)-毛壳菌素目前最高效、最快捷(4步)的对映选择性全合成,(+)-栗精胺的高效、高立体选择性全合成(9步),以及海洋大环天然产物(-)-haliclonin A的首次全合成来展示这一拓展的价值和意义,并提出对映选择性仿生合成应该是未来仿生合成发展的方向.
Three classics in biomimetic synthesis were revisited:Robinson's one-step total synthesis of tropinone,Heathcock's biomimetic racemic total synthesis of Daphniphyllum alkaloids,and Husson's four-step enantioselective total synthesis of(+)-isonitramine.Further inspection of these achievements allows appreciating the art of biomimetic total synthesis and their impact on organic chemistry.In this regard,an extension of the biomimetic synthesis defined by Breslow was suggested:to cover the imitation of strategies used by the biosystems in biosynthesis.The value of the extended concept of biomimetic synthesis was showcased by three enantioselective total syntheses accomplished in our research group:the shortest and the most efficient four-step enantioselective total synthesis of(-)-chaetominine,the highly efficient and stereoselective synthesis of(+)-castanospermine,and the first total synthesis of(-)-haliclonin A.These progress afford the opportunity to plot the direction for future development:enantioselective biomimetic total synthesis.