Valorization of Ethanol: Ruthenium-Catalyzed Guerbet and Sequential Functionalization Processes

We report a ruthenium-catalyzed tandem Guerbet-alkylation strategy for the valorization of ethanol. The products ofethanol upgrading (higher-order alcohols) undergo subsequent C-Cbond forming reactions with four carbon pronucleophiles and one ylide.Studies into catalyst design led to the development of ClRu(5-Mebpi)(PPh3)2(bpi = 1,3-bis(2 '-pyridylimino)isoindolate) as a highlyefficient catalyst for producing biofuels and value-added chemicals fromethanolviaGuerbet and tandem Guerbet reactions. This catalyst affords65% higher-order alcohols in short reaction times (2 h), providing thehighest TON (155,890) and TOF (12,690 h-1) for a homogeneous catalyst reported to date.

Automated summary

We report a ruthenium-catalyzed tandem Guerbet-alkylation strategy for the valorization of ethanol. The development of ClRu(5-Mebpi)(PPh3)2(bpi = 1,3-bis(2 '-pyridylimino)isoindolate) catalyst led to the efficient production of higher-order alcohols from ethanol in short reaction times (2 h), achieving the highest TON (155,890) and TOF (12,690 h-1) for a homogeneous catalyst reported so far.