Scorpionate Catalysts for Coupling CO2 and Epoxides to Cyclic Carbonates: A Rational Design Approach for Organocatalysts

• Published in: Journal of organic chemistry Vol. 83; no. 16; pp. 9370 - 9380
• Main Authors: Hong, Mannkyu, Kim, Yoseph, Kim, Hyejin, Cho, Hee Jin, Baik, Mu-Hyun, Kim, Youngjo
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 17.08.2018; Amer Chemical Soc
• Subjects: Chemistry; Chemistry, Organic; Physical Sciences; Science & Technology; SOLVATION FREE-ENERGIES; MOLECULAR CALCULATIONS; LIGANDS; EFFECTIVE CORE POTENTIALS; CONVERSION; ORGANIC CARBONATES; METAL; MOLYBDENUM(VI) DIOXO COMPLEXES; COPOLYMERIZATION; FIXATION
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/acs.joc.8b00722

Novel scorpionate-type organocatalysts capable of effectively coupling carbon dioxide and epoxides under mild conditions to afford cyclic propylene carbonates were developed. On the basis of a combined experimental and computational study, a precise mechanistic proposal was developed and rational optimization strategies were identified. The epoxide ring-opening, which requires an iodide as a nucleophile, was enhanced by utilizing an immonium functionality that can form an ion pair with iodide, making the ring-opening process intramolecular. The CO2 activation and cyclic carbonate formation were catalyzed by the concerted action of two hydrogen bonds originating from two phenolic groups placed at the claw positions of the scorpionate scaffold. Electronic tuning of the hydrogen bond donors allowed to identify a new catalyst that can deliver >90% yield for a variety of epoxide substrates within 7 h at room temperature under a CO2 pressure of only 10 bar, and is highly recyclable.