Citation: Gao Yan-Jiao, Luo Shi-Peng, Ye Jian-Liang, Huang Pei-Qiang. An attempted approach to the tricyclic core of haliclonin A:Structural elucidation of the final product by 2D NMR[J]. Chinese Chemical Letters, ;2017, 28(6): 1176-1181. doi: 10.1016/j.cclet.2017.04.016 shu

An attempted approach to the tricyclic core of haliclonin A:Structural elucidation of the final product by 2D NMR

Department of Chemistry, Fujian Provincial Key Laboratory of Chemical Biology, iChEM(Collaborative Innovation Center of Chemistry for Energy Materials), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China

Corresponding author: Huang Pei-Qiang, pqhuang@xmu.edu.cn
Received Date: 21 February 2017
Revised Date: 13 April 2017
Accepted Date: 13 April 2017
Available Online: 21 June 2017

Figures(5)

We describe the design and execution of a novel synthetic route to the tricyclic core of haliclonin A, a tetracyclic marine natural product. The approach features Bachi's thiol-medicated free radical cyclization of alkenyl isocyanide to build the bridged ring system, and ring-closing metathesis (RCM) reaction to form the macrocycle. Execution of the synthetic plan ultimately resulted in a diazatricyclic compound. By means of 2D NMR techniques, the structure of this compound was revealed to an unexpected product 8. Analysis of the synthetic pathways allowed concluding that the unexpected product is a result of an "unexpected" migration of olefinic bond during dioxolanation of the 2-cyclohexenone derivative 7. This investigation also resulted in a concise construction of the functionalized hexahydro-1H-isoindole-1, 5 (4H)-dione 12 and the macrocyclic tricyclic ring system 8.
- 2D NMR,
- Ring closing metathesis,
- Macrocycles,
- Lactams,
- Structure revision,
- Cyclization
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