Enantioselective Total Synthesis and Structural Revision of (－)-Isochaetominine

doi:10.6023/cjoc201512015

Chin. J. Org. Chem. ›› 2016, Vol. 36 ›› Issue (2): 315-324.DOI: 10.6023/cjoc201512015 Previous Articles Next Articles

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(－)-Isochaetominine推测结构的对映选择性全合成与结构修正

黄培强, 茅中一, 耿辉

福建省化学生物学重点实验室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

收稿日期:2015-12-10 发布日期:2015-12-15
通讯作者: 黄培强 E-mail:pqhuang@xmu.edu.cn
基金资助:
国家自然科学基金(No. 21472153)和教育部长江学者和创新团队发展计划资助项目

Enantioselective Total Synthesis and Structural Revision of (－)-Isochaetominine

Huang Peiqiang, Mao Zhongyi, Geng Hui

Fujian Provincial Key Laboratory of Chemical Biology, Collaborative Innovation Centre of Chemistry for Energy Materials, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005

Received:2015-12-10 Published:2015-12-15
Supported by:
Project supported by the National Natural Science Foundation of China (No. 21472153) and the Program for Changjiang Scholars and Innovative Research Team in University of Ministry of Education

1. Enantioselective Total Synthesis and Structural Revision of (－)-Isochaetominine.PDF(2472KB)

Abstract

In this paper, the enantioselective total synthesis and structure revision of the proposed structure of isochaetominine 8 are described. On the basis of the stereodivergent strategy, a highly efficient five-step synthesis of the proposed structure of isochaetominine 8 and its diastereomer (+)-2,3,14-tri-epi-chaetominine (12) was achieved. The method features the use of L-tryptophan and L-alanine benzyl ester as the starting materials, and a dimethyldioxirane (DMDO)-triggered tandem reaction as a key step. A comparison of the physical and spectral data of the natural isochaetominine with those of the diastereomers obtained during our previous stereodivergent synthesis of chaetominine (1), allowed revising the structure of isochaetominine as (－)-11-epi-chaetominine (18). The first enantioselective total synthesis of this natural product has been accomplished previously in our laboratories in five steps, 31.6% overall yield from L-tryptophan. Besides, an investigation on the L-tryptophan and L-valine tert-butyl ester-based synthesis of isochaetominine C resulted in a stereodivergent synthesis of three diastereomers of isochaetominine C. Finally, it was revealed that attempted site selective epimerization at C(14) of 13B led to a bis-epimerization at both C(14) and C(11).

Key words: alkaloids, isochaetominine, total synthesis, structural revision, stereodivergent synthesis, epimerization

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Huang Peiqiang, Mao Zhongyi, Geng Hui. Enantioselective Total Synthesis and Structural Revision of (－)-Isochaetominine[J]. Chin. J. Org. Chem., 2016, 36(2): 315-324.

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(－)-Isochaetominine推测结构的对映选择性全合成与结构修正

Enantioselective Total Synthesis and Structural Revision of (－)-Isochaetominine

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