Metalloporphyrin-Based Hypercrosslinked Polymers Catalyze Hetero-Diels-Alder Reactions of Unactivated Aldehydes with Simple Dienes: A Fascinating Strategy for the Construction of Heterogeneous Catalysts

Zhiyu Dou; Li Xu; Yongfeng Zhi; Yuwei Zhang; Hong Xia; Ying Mu; Xiaoming Liu

doi:10.1002/chem.201601151

Metalloporphyrin-Based Hypercrosslinked Polymers Catalyze Hetero-Diels-Alder Reactions of Unactivated Aldehydes with Simple Dienes: A Fascinating Strategy for the Construction of Heterogeneous Catalysts

Chemistry. 2016 Jul 11;22(29):9919-22. doi: 10.1002/chem.201601151. Epub 2016 Jun 8.

Authors

Zhiyu Dou¹, Li Xu^{2

3}, Yongfeng Zhi², Yuwei Zhang², Hong Xia⁴, Ying Mu², Xiaoming Liu⁵

Affiliations

¹ Department of Chemistry and Chemical Engineering, Changchun University of Science and Technology, Changchun, 130022, P. R. China. douzhiyu79@sina.cn.
² State Key Laboratory for Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun, 130012, P. R. China.
³ Department of Chemistry and Chemical Engineering, Changchun University of Science and Technology, Changchun, 130022, P. R. China.
⁴ State Key Laboratory on Integrated Optoelectronics, College of Electronic Science and Technology, Jilin University, Changchun, 130012, P. R. China.
⁵ State Key Laboratory for Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun, 130012, P. R. China. xm_liu@jlu.edu.cn.

PMID: 27147500
DOI: 10.1002/chem.201601151

Abstract

We describe a novel and intriguing strategy for the construction of efficient heterogeneous catalysts by hypercrosslinking catalyst molecules in a one-pot Friedel-Crafts alkylation reaction. The new hypercrosslinked polymers (HCPs) as porous solid catalysts exhibit the combined advantages of homogeneous and heterogeneous catalysis, owing to their high surface area, good stability, and tailoring of catalytic centers on the frameworks. Indeed, a new class of metalloporphyrin-based HCPs were successfully synthesized using modified iron(III) porphyrin complexes as building blocks, and the resulting networks were found to be excellent recyclable heterogeneous catalysts for the hetero-Diels-Alder reaction of unactivated aldehydes with 1,3-dienes. Moreover, this new strategy showed wide adaptability, and many kinds of homogeneous-like solid-based catalysts with high catalytic performance and excellent recyclability were also constructed.

Keywords: hetero-Diels-Alder reaction; heterogeneous catalysis; hypercrosslinked polymers; metalloporphyrin-based networks; polymers.