Chinese Journal of Organic Chemistry >
Enantioselective Total Synthesis and Structural Revision of (－)-Isochaetominine
Received date: 2015-12-10
Online 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
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).
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
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[43] After arriving at the conclusions of this paper, we informed the corresponding author of the reference 36 about the correct structure of the natural isochaetominine. In line with the information we provided, the authors prepared a single crystal of the natural isochaetominine and determined its structure by X-ray diffraction analysis. Their new result confirmed our conclusions. For the corrections to the Ref.
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