Ir(triscarbene)‐catalyzed sustainable transfer hydrogenation of levulinic acid to γ‐valerolactone

• Published in: Applied organometallic chemistry Vol. 35; no. 2
• Main Authors: Sung, Kihyuk, Lee, Mi‐hyun, Cheong, Yeon‐Joo, Jang, Hye‐Young
• Format: Journal Article
• Language: English
• Published: Chichester Wiley Subscription Services, Inc 01-02-2021
• Subjects: Catalysts; Chemistry; Deuterium; Ethanol; Ethylene glycol; Glycerol; Hydrides; Hydrogenation; Iridium; iridium complex; Levulinic acid; Propylene; Reaction mechanisms; Recyclability; sustainable reaction; transfer hydrogenation; triscarbene ligand; γ‐valerolactone
• ISSN: 0268-2605; 1099-0739
• DOI: 10.1002/aoc.6105

Sustainable iridium‐catalyzed transfer hydrogenation using glycerol as the hydride source was employed to convert levulinic acid to γ‐valerolactone (GVL) with exceptionally high turnover numbers (TONs) (500,000) and turnover frequencies (TOFs) (170,000 h−1). The highly efficient triscarbene‐modified iridium catalysts demonstrated good catalytic activities with low catalyst loadings (0.7 ppm) and good recyclability with an accumulated TON of over two million in the fourth reaction. In addition to glycerol, propylene glycol (PG), ethylene glycol (EG), isopropanol (IPA), and ethanol (EtOH) successfully transferred hydrides to levulinic acid, producing GVL with TONs of 339,000 (PG), 242,000 (EG), 334,000 (IPA), and 208,000 (EtOH), respectively. Deuterium‐labeling experiments were conducted to gain insight into the reaction mechanism.
Ir(triscarbene) catalysts promoted the conversion of biomass‐derived levulinic acid to γ‐valerolactone under sustainable transfer hydrogenation conditions using biomass‐derived alcohols.