Cyclopropenimine-Mediated CO Activation for the Synthesis of Polyurethanes and Small-Molecule Carbonates and Carbamates

Overview

Journal Angew Chem Int Ed Engl

Specialty Chemistry

Date 2024 Mar 10

PMID 38462499

Authors

Dino Wu

Robert T Martin

Jeanette Pina

Junho Kwon

Michael P Crockett

Andy A Thomas

Osvaldo Gutierrez

Nathaniel H Park

James L Hedrick

Luis M Campos

Affiliations

Soon will be listed here.

Abstract

Carbon dioxide (CO) is an abundant C1 feedstock with tremendous potential to produce versatile building blocks in synthetic applications. Given the adverse impact of CO on the atmosphere, it is of paramount importance to devise strategies for upcycling it into useful materials, such as polymers and fine chemicals. To activate such stable molecule, superbases offer viable modes of binding to CO. In this study, a superbase cyclopropenimine derivative was found to exhibit exceptional proficiency in activating CO and mediating its polymerization at ambient temperature and pressure for the synthesis of polyurethanes. The versatility of this reaction can be extended to monofunctional amines and alcohols, yielding a variety of functional carbonates and carbamates.

Citing Articles

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References

Bandar J, Lambert T . Cyclopropenimine-catalyzed enantioselective Mannich reactions of tert-butyl glycinates with N-Boc-imines. J Am Chem Soc. 2013; 135(32):11799-802. PMC: 3804837. DOI: 10.1021/ja407277a. View

Bai Y, Cheng M, Zheng X, Zhang S, Wang P . Chiral Cyclopropenimine-catalyzed Asymmetric Michael Addition of Bulky Glycine Imine to α,β-Unsaturated Isoxazoles. Chem Asian J. 2022; 17(11):e202200131. DOI: 10.1002/asia.202200131. View

Chen J, McGraw M, Chen E . Diverse Catalytic Systems and Mechanistic Pathways for Hydrosilylative Reduction of CO. ChemSusChem. 2019; 12(20):4543-4569. DOI: 10.1002/cssc.201901764. View

Dabral S, Bayarmagnai B, Hermsen M, Schiessl J, Mormul V, Hashmi A . Silver-Catalyzed Carboxylative Cyclization of Primary Propargyl Alcohols with CO. Org Lett. 2019; 21(5):1422-1425. DOI: 10.1021/acs.orglett.9b00156. View

Bandar J, Barthelme A, Mazori A, Lambert T . Structure-Activity Relationship Studies of Cyclopropenimines as Enantioselective Brønsted Base Catalysts. Chem Sci. 2015; 6(2):1537-1547. PMC: 4618405. DOI: 10.1039/C4SC02402H. View

Seipp C, Williams N, Kidder M, Custelcean R . CO Capture from Ambient Air by Crystallization with a Guanidine Sorbent. Angew Chem Int Ed Engl. 2016; 56(4):1042-1045. DOI: 10.1002/anie.201610916. View

Sakakura T, Choi J, Yasuda H . Transformation of carbon dioxide. Chem Rev. 2007; 107(6):2365-87. DOI: 10.1021/cr068357u. View

Jeske R, Rowley J, Coates G . Pre-rate-determining selectivity in the terpolymerization of epoxides, cyclic anhydrides, and CO2: a one-step route to diblock copolymers. Angew Chem Int Ed Engl. 2008; 47(32):6041-4. DOI: 10.1002/anie.200801415. View

Deacy A, Kilpatrick A, Regoutz A, Williams C . Understanding metal synergy in heterodinuclear catalysts for the copolymerization of CO and epoxides. Nat Chem. 2020; 12(4):372-380. DOI: 10.1038/s41557-020-0450-3. View

10.

Lu X, Darensbourg D . Cobalt catalysts for the coupling of CO2 and epoxides to provide polycarbonates and cyclic carbonates. Chem Soc Rev. 2011; 41(4):1462-84. DOI: 10.1039/c1cs15142h. View

11.

Morodo R, Dumas D, Zhang J, Lui K, Hurst P, Bosio R . Ring-Opening Polymerization of Cyclic Esters and Carbonates with (Thio)urea/Cyclopropenimine Organocatalytic Systems. ACS Macro Lett. 2024; :181-188. DOI: 10.1021/acsmacrolett.3c00716. View

12.

Ghosh A, Brindisi M . Organic carbamates in drug design and medicinal chemistry. J Med Chem. 2015; 58(7):2895-940. PMC: 4393377. DOI: 10.1021/jm501371s. View

13.

Yang G, Zhang Y, Xie R, Wu G . Scalable Bifunctional Organoboron Catalysts for Copolymerization of CO and Epoxides with Unprecedented Efficiency. J Am Chem Soc. 2020; 142(28):12245-12255. DOI: 10.1021/jacs.0c03651. View

14.

Heldebrant D, Jessop P, Thomas C, Eckert C, Liotta C . The reaction of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) with carbon dioxide. J Org Chem. 2005; 70(13):5335-8. DOI: 10.1021/jo0503759. View

15.

Rauch M, Strater Z, Parkin G . Selective Conversion of Carbon Dioxide to Formaldehyde via a Bis(silyl)acetal: Incorporation of Isotopically Labeled C Moieties Derived from Carbon Dioxide into Organic Molecules. J Am Chem Soc. 2019; 141(44):17754-17762. DOI: 10.1021/jacs.9b08342. View

16.

Stukenbroeker T, Bandar J, Zhang X, Lambert T, Waymouth R . Cyclopropenimine Superbases: Competitive Initiation Processes in Lactide Polymerization. ACS Macro Lett. 2016; 4(8):853-856. PMC: 4762272. DOI: 10.1021/acsmacrolett.5b00421. View

17.

Bandar J, Lambert T . Enantioselective Brønsted base catalysis with chiral cyclopropenimines. J Am Chem Soc. 2012; 134(12):5552-5. DOI: 10.1021/ja3015764. View

18.

Kember M, Buchard A, Williams C . Catalysts for CO2/epoxide copolymerisation. Chem Commun (Camb). 2010; 47(1):141-63. DOI: 10.1039/c0cc02207a. View

19.

Banik J, Chakraborty D, Rizwan M, Shaik A, Chandan M . Review on disposal, recycling and management of waste polyurethane foams: A way ahead. Waste Manag Res. 2023; 41(6):1063-1080. DOI: 10.1177/0734242X221146082. View

20.

Zhang D, Boopathi S, Hadjichristidis N, Gnanou Y, Feng X . Metal-Free Alternating Copolymerization of CO2 with Epoxides: Fulfilling "Green" Synthesis and Activity. J Am Chem Soc. 2016; 138(35):11117-20. DOI: 10.1021/jacs.6b06679. View