One-pot Enantioselective Multi-component Cascade Reactions for Synthesis of Chiral Functionalized Hydro-epoxyisochromenes: A Rapid Access toMolecular Complexity

doi:10.6023/A15090627

Acta Chim. Sinica ›› 2016, Vol. 74 ›› Issue (1): 54-60.DOI: 10.6023/A15090627 Previous Articles Next Articles

Article

“一锅法”不对称多组分串联反应合成手性氢化环氧异色烯衍生物:一种快速构建分子复杂性方法

唐敏, 吴永, 刘源, 蔡茂强, 夏飞, 刘顺英, 胡文浩

华东师范大学化学与分子工程学院上海分子治疗与新药创制工程技术研究中心上海 200062

投稿日期:2015-09-25 发布日期:2015-11-19
通讯作者: 刘顺英, 胡文浩 E-mail:syliu@sist.ecnu.edu.cn;whu@chem.ecnu.edu.cn
基金资助:
项目受国家杰出青年基金(No. 21125209)、国家自然基金重点项目(No. 21332003)、科技部973课题(No. 2011CB808600)和上海市科委重点项目(No. 12JC1403800)资助.

One-pot Enantioselective Multi-component Cascade Reactions for Synthesis of Chiral Functionalized Hydro-epoxyisochromenes: A Rapid Access toMolecular Complexity

Tang Min, Wu Yong, Liu Yuan, Cai Maoqiang, Xia Fei, Liu Shunying, Hu Wenhao

Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062

Received:2015-09-25 Published:2015-11-19
Supported by:
Project supported by the National Natural Science Foundation of China (Nos. 21125209 and 21332003), Ministry of science and Technology of the Peoples's Republic of China (No. 2011CB808600), Science and Technology Commission of Shanghai Municipality (No. 12JC1403800).

1. One-pot Enantioselective Multi-component Cascade Reactions for Synthesis of Chiral Functionalized Hydro-epoxyisochromenes: A Rapid Access toMolecular Complexity.PDF(2413KB)

Abstract

An Rh₂(OAc)₄/Zr-3-I-binol co-catalyzed enantioselective three-component cascade reaction of diazo compounds, ethyl 4-hydroxybutenoate and furfurals has been designed to build complex fused O-heterocycles in a one pot fashion. The reaction was conducted in CH₂Cl₂ or CHCl₃ at ambient temperature with 3 Å molecular sieves as an additive. The multi- component process was completed within 3 h to give multi-component products and the following Diels-Alder (DA) cyclization product was observed in the next several hours. It was found that the DA process was slow but could be completed after 7～12 d by standing the crude reaction mixture after evaporating solvent. Following a one-pot epoxidation of the product further increases the molecular complexity to give fused epoxidation products bearing multiple chiral carbon centers. Especially to be noted, all of the products are very easy to be purified by simple recrystallization in mixture solvent of ethyl acetate (EA)/petroleum ether (PE, 60～90 ℃) and do not need any column chromatography method. Using the developed method, hydroepoxyisochromene derivatives with up to eight contiguous chiral carbon centers have been readily prepared from simple starting materials with high diastereoselectivity (up to 99/1 dr) and enantioselectivity (up to 99% ee). The absolute stereochemistry of product was determined by the single crystal X-ray analysis as a chair conformation with absolute configurations. The possible mechanisms were theoretically investigated by DFT calculation and proposed as an oxonium ylide-trapping three-component reaction subsequently followed with a spontaneous intramolecular Diels-Alder process and an epoxidation at the end. The developed three-component cascade reaction provides a rapid access to the construction of chiral fused polycyclic O-heterocycles with molecular complexity.

Key words: multi-component cascade reaction, asymmetric catalysis, molecular complexity, one pot, O-heterocycles

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Tang Min, Wu Yong, Liu Yuan, Cai Maoqiang, Xia Fei, Liu Shunying, Hu Wenhao. One-pot Enantioselective Multi-component Cascade Reactions for Synthesis of Chiral Functionalized Hydro-epoxyisochromenes: A Rapid Access toMolecular Complexity[J]. Acta Chim. Sinica, 2016, 74(1): 54-60.

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“一锅法”不对称多组分串联反应合成手性氢化环氧异色烯衍生物:一种快速构建分子复杂性方法

One-pot Enantioselective Multi-component Cascade Reactions for Synthesis of Chiral Functionalized Hydro-epoxyisochromenes: A Rapid Access toMolecular Complexity

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