Citation: Huang Peiqiang, Mao Zhongyi, Geng Hui. Enantioselective Total Synthesis and Structural Revision of (－)-Isochaetominine[J]. Chinese Journal of Organic Chemistry, ;2016, 36(2): 315-324. doi: 10.6023/cjoc201512015 shu

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

1.
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

Corresponding author: Huang Peiqiang,
Received Date: 10 December 2015

Fund Project: 国家自然科学基金(No. 21472153) (No. 21472153)

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).
- alkaloids,
- isochaetominine,
- total synthesis,
- structural revision,
- stereodivergent synthesis,
- epimerization
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