Synthesis of the ABC Ring System of Wallichanol Natural Product

doi:10.6023/cjoc202008001

Chinese Journal of Organic Chemistry ›› 2021, Vol. 41 ›› Issue (2): 726-730.DOI: 10.6023/cjoc202008001 Previous Articles Next Articles

Article

Wallichanol类天然产物ABC环系合成研究

杨刚^a^,^b, 冯翔宇^a^,^b, 韩丛丛^a^,^b, 陈洋^c^,^*(), 何述钟^a^,^b^,^*()

a 贵州大学药学院贵阳 550025
b 贵州省合成药物工程实验室贵阳 550025
c 贵州大学精细化工研究开发中心绿色农药与农业生物工程国家重点实验室培育基地教育部绿色农药物工程重点实验室贵阳 550025

收稿日期:2020-08-01 修回日期:2020-09-17 发布日期:2020-10-12
通讯作者: 陈洋, 何述钟
作者简介:
* Corresponding authors. E-mail: szhe@gzu.edu.cn; ychen1@gzu.edu.cn
基金资助:
国家自然科学基金(21562011); 国家自然科学基金(21861010); 贵州省科技基金([2015]2047); 贵州省科技基金([2020]1Y108); 贵州省科技基金([2018]5781); 贵州省研究生教育案例库建设(KCALK2017012); 贵州大学人才工程([2014]36)

Synthesis of the ABC Ring System of Wallichanol Natural Product

Gang Yang^a^,^b, Xiangyu Feng^a^,^b, Congcong Han^a^,^b, Yang Chen^c^,^*(), Shuzhong He^a^,^b^,^*()

a School of Pharmaceutical Sciences, Guizhou University, Guiyang 550025
b Guizhou Engineering Laboratory for Synthetic Drugs, Guiyang 550025
c State Key Laboratory Breeding Base of Green Pesticide and Agricultural Bioengineering, Key Laboratory of Green Pesticide and Agriculture Bioengineering, Ministry of Education, Center for Research and Development of Fine Chemicals, Guizhou University, Guiyang 550025

Received:2020-08-01 Revised:2020-09-17 Published:2020-10-12
Contact: Yang Chen, Shuzhong He
Supported by:
the National Natural Science Foundation of China(21562011); the National Natural Science Foundation of China(21861010); the Science and Technology Foundation of Guizhou Province([2015]2047); the Science and Technology Foundation of Guizhou Province([2020]1Y108); the Science and Technology Foundation of Guizhou Province([2018]5781); the Case Base Construction Project for Guizhou Graduate Education(KCALK2017012); the Guizhou University Talent Project([2014]36)

1. cjoc202008001辅助材料.pdf(1996KB)

Abstract

A rapid construction of the ABC ring of wallichanol is described. The synthesis features an efficient Diels-Alder reaction for the bicyclo[2.2.2]octane synthesis and a gold-catalyzed alkyne carbometalation for the cyclobutane synthesis. The overall yield of this 7-stepped synthesis is 42%. This strategy can pave the road towards the total synthesis of wallichanol.

Key words: wallichanol, Diels-Alder reaction, carbometalation, total synthesis

Cite this article

Gang Yang, Xiangyu Feng, Congcong Han, Yang Chen, Shuzhong He. Synthesis of the ABC Ring System of Wallichanol Natural Product[J]. Chinese Journal of Organic Chemistry, 2021, 41(2): 726-730.

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References 12

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Entry	Catalysis	Solvent	Time	Yield/% (endo∶exo)
1	Ph₃PAuCl (5 mol%)	V(DCM)∶V(MeOH)=10∶1	12 h	38 (1∶10)
2	Ph₃PAuCl (10 mol%)	V(DCM)∶V(MeOH)=10∶1	12 h	65 (1∶10)
3	Ph₃PAuNTf₂ (10 mol%)	V(DCM)∶V(MeOH)=10∶1	12 h	63 (4.6∶10)
4	Ph₃PAuCl (5 mol%)/AgBF₄ (5 mol%)	V(DCM)∶V(MeOH)=10∶1	15 min	46 (1∶10)
5	Ph₃PAuNTf₂ (5 mol%)/AgBF₄ (5 mol%)	V(DCM)∶V(MeOH)=10∶1	30 min	44 (4.6∶10)
6	Ph₃PAuCl (10 mol%)/AgBF₄ (10 mol%)	V(DCM)∶V(MeOH)=10∶1	15 min	78 (1∶10)
7	Ph₃PAuCl (10 mol%)/AgBF₄ (10 mol%)	V(DCM)∶V(MeOH)=10∶1	15 min	68 (1∶10)
8	Ph₃PAuNTf₂ (10 mol%)/AgBF₄ (10 mol%)	V(DCM)∶V(MeOH)=10∶1	30 min	75 (4.6∶10)

Entry	Catalysis	Solvent	Time	Yield/% (endo∶exo)
1	Ph₃PAuCl (5 mol%)	V(DCM)∶V(MeOH)=10∶1	12 h	38 (1∶10)
2	Ph₃PAuCl (10 mol%)	V(DCM)∶V(MeOH)=10∶1	12 h	65 (1∶10)
3	Ph₃PAuNTf₂ (10 mol%)	V(DCM)∶V(MeOH)=10∶1	12 h	63 (4.6∶10)
4	Ph₃PAuCl (5 mol%)/AgBF₄ (5 mol%)	V(DCM)∶V(MeOH)=10∶1	15 min	46 (1∶10)
5	Ph₃PAuNTf₂ (5 mol%)/AgBF₄ (5 mol%)	V(DCM)∶V(MeOH)=10∶1	30 min	44 (4.6∶10)
6	Ph₃PAuCl (10 mol%)/AgBF₄ (10 mol%)	V(DCM)∶V(MeOH)=10∶1	15 min	78 (1∶10)
7	Ph₃PAuCl (10 mol%)/AgBF₄ (10 mol%)	V(DCM)∶V(MeOH)=10∶1	15 min	68 (1∶10)
8	Ph₃PAuNTf₂ (10 mol%)/AgBF₄ (10 mol%)	V(DCM)∶V(MeOH)=10∶1	30 min	75 (4.6∶10)

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Wallichanol类天然产物ABC环系合成研究

Synthesis of the ABC Ring System of Wallichanol Natural Product

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