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. 2020 Jul 1;12(26):29212-29217.
doi: 10.1021/acsami.0c04957. Epub 2020 Jun 23.

(Thio)urea-Based Covalent Organic Framework as a Hydrogen-Bond-Donating Catalyst

Jiyun Hu  1 , Federica Zanca  2 , Patricia Lambe  1 , Miu Tsuji  1 , Samantha Wijeweera  1 , Stefano Todisco  3 , Piero Mastrorilli  3 , William Shirley  4 , Mourad Benamara  5 , Peyman Z Moghadam  2 , Hudson Beyzavi  1
Affiliations

(Thio)urea-Based Covalent Organic Framework as a Hydrogen-Bond-Donating Catalyst

Jiyun Hu et al. ACS Appl Mater Interfaces. .

Abstract

Two-dimensional urea- and thiourea-containing covalent organic frameworks (COFs) were synthesized at ambient conditions at large scale within 1 h in the absence of an acid catalyst. The site-isolated urea and thiourea in the COF showed enhanced catalytic efficiency as a hydrogen-bond-donating organocatalyst compared to the molecular counterparts in epoxide ring-opening reaction, aldehyde acetalization, and Friedel-Crafts reaction. The COF catalysts also had excellent recyclability.

Keywords: catalyst quenching; covalent organic frameworks; hydrogen-bond-donating catalyst; site isolation; thiourea.

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Conflict of interest statement

The authors declare no competing financial interests.

Figures

Figure 1.
Figure 1.
Chain structure by N–H…O and N–H…S hydrogen bonding of diphenylurea (left) and diphenylthiourea (right) respectively in the solid state.
Figure 2.
Figure 2.
(a) Experimental and simulated PXRD pattern of COF-TpU and COF-TpTU; Simulated eclipsed structure of COF-TpU (b) and COF-TpTU (c).
Figure 3.
Figure 3.
COF-TpTU as HBD catalyst for acetalization reaction, and Friedel-Crafts reaction. Reaction conditions: A) Benzaldehyde (0.5 mmol) and COF-TpTU (5 mol%) in dry methanol (1 mL) were stirred at 40 °C for 11 h; B) β-nitrostyrene (0.2 mmol), N-methylpyrrole (1.0 mmol) and COF-TpTU (10 mol%) in CH3CN (0.5 mL) were stirred at 80 °C for 48 h.
Scheme 1.
Scheme 1.
Synthesis of urea and thiourea containing COFs.
Scheme 2.
Scheme 2.
Regioselective and enantioretentive methanolysis of styrene oxide catalyzed by COF-TpTU.
See this image and copyright information in PMC

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