(－)-Isochaetominine推测结构的对映选择性全合成与结构修正

doi:10.6023/cjoc201512015

有机化学 ›› 2016, Vol. 36 ›› Issue (2): 315-324.DOI: 10.6023/cjoc201512015 上一篇下一篇

研究论文

(－)-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

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摘要/Abstract

报道生物碱isochaetominine推测结构8的对映选择性全合成与结构修正. 采用立体多样性合成策略, 通过L-色氨酸与L-丙氨酸苄酯组合, 以DMDO氧化启动的串联反应为关键反应, 经5步高效地完成了isochaetominine推测结构8及其立体异构体(+)-2,3,14-tri-epi-chaetominine (12)的全合成. 基于本实验室此前有关毛壳菌素(1)立体多样性合成的工作, 天然isochaetominine的结构修正为(－)-11-epi-chaetominine (18). 我们此前已完成了该天然产物的首次对映选择性全合成(从L-色氨酸出发, 5步, 总产率31.6%). 此外, 通过研究色氨酸与缬氨酸叔丁酯组合, 建立了isochaetominine C三个非对映立体异构体的立体多样性合成. 最后, 证实了化合物13B无法进行C(14)位定点差向异构化, 但可以进行C(11)和C(14)双差向异构化.

关键词: 生物碱, isochaetominine, 全合成, 结构修正, 立体多样性合成, 差向异构化

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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黄培强, 茅中一, 耿辉. (－)-Isochaetominine推测结构的对映选择性全合成与结构修正[J]. 有机化学, 2016, 36(2): 315-324.

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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