Enhancing Ru-Catalyzed Guerbet Reactivity for Biofuel Production from Ethanol

13 December 2022, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


We recently reported the development of an N,N,N-pincer Ru catalyst ClRu(5-Mebpi)(PPh3)2 (bpi = 1,3-bis(2′-pyridylimino)isoindolate) for the efficient production of advanced biofuels from ethanol via the Guerbet reaction. This catalyst provided 65 % yield and C4-C8 alcohols and the current highest TON (155,890) and TOF (12,690 h-1) reported for a homogenous, single-site Guerbet catalyst. Through mechanism guided catalyst re-design, we have further enhanced the reactivity of these catalysts via selective ligand modifications, leading to the development of two new catalysts. ClRu(5-OMebpi)(PPh3)2 and ClRu(5-tBubpi)(PPh3)2 provide 74 % and 76 % yields of higher order alcohols respectively - both representing the best-in-class homogenous catalysts for conducting Guerbet chemistry to date.


Aldol Condensation
Metal Carbonyl
Primary Alcohol


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