Mechanistic Study of a One-Step Catalytic Conversion of Fructose to 2,5-Dimethyltetrahydrofuran

Carbohydrates, such as fructose, can be fully dehydroxylated to 2,5-dimethyltetrahydrofuran (DMTHF), a valuable chemical and potential gasoline substitute, by the use of a dual catalytic system consisting of HI and RhX3 (X=Cl, I). A mechanistic study has been carried out to understand the roles that both acid and metal play in the reaction. HI serves a two-fold purpose: HI acts as a dehydration agent (loss of 3 H2O) in the initial step of the reaction, and as a reducing agent for the conjugated carbinol group in a subsequent step. I2 is formed in the reduction step and metal-catalyzed hydrogenation reforms HI. The rhodium catalyst, in addition to catalyzing the reaction of iodine with hydrogen, functions as a hydrogenation catalyst for C?O and C?C bonds. A general mechanistic scheme for the overall reaction is proposed based on identification of intermediates, independent reactions of the intermediates, and deuterium labeling studies.