Raising the Asymmetric Catalytic Efficiency of Chiral Covalent Organic Frameworks by Tuning the Pore Environment

Zhang, Kai; Tang, Xihao; Yang, Xi; Wu, Jialin; Guo, Baoying; Xiao, Rui; Xie, Yao; Zheng, Shengrun; Jiang, Huawei; Fan, Jun; Zhang, Weiguang; Liu, Yi; Cai, Songliang

doi:10.1021/acsami.3c17048

Raising the Asymmetric Catalytic Efficiency of Chiral Covalent Organic Frameworks by Tuning the Pore Environment

Journal Article · Mon Feb 19 23:00:00 EST 2024 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.3c17048· OSTI ID:2500819

Zhang, Kai ^[1]; Tang, Xihao ^[1]; Yang, Xi ^[1]; Wu, Jialin ^[1]; Guo, Baoying ^[1]; Xiao, Rui ^[1]; Xie, Yao ^[1]; Zheng, Shengrun ^[2]; Jiang, Huawei ^[2]; ^[2]; ^[2]; ^[3]; ^[2]

South China Normal University (SCNU), Guangzhou (China)
South China Normal University (SCNU), Guangzhou (China); SCNU Qingyuan Institute of Science and Technology Innovation Co., Ltd., Qingyuan (China)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry

Chiral covalent organic frameworks (COFs) hold considerable promise in the realm of heterogeneous asymmetric catalysis. However, fine-tuning the pore environment to enhance both the activity and stereoselectivity of chiral COFs in such applications remains a formidable challenge. In this study, we have successfully designed and synthesized a series of clover-shaped, hydrazone-linked chiral COFs, each with a varying number of accessible chiral pyrrolidine catalytic sites. Remarkably, the catalytic efficiencies of these COFs in the asymmetric aldol reaction between cyclohexanone and 4-nitrobenzaldehyde correlate well with the number of accessible pyrrolidine sites within the frameworks. Further, the COF featuring nearly one pyrrolidine moiety at each nodal point demonstrated excellent reaction yields and enantiomeric excess (ee) values, reaching up to 97 and 83%, respectively. The findings not only underscore the profound impact of a deliberately controlled chiral pore environment on the catalytic efficiencies of COFs but also offer a new perspective for the design and synthesis of advanced chiral COFs for efficient asymmetric catalysis.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Natural Science Foundation of China (NSFC); Natural Science Foundation of Guangdong Province

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 2500819

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 8 Vol. 16; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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