Chemistry: A European Journal 2012-09-24

Mechanistic study of a one-step catalytic conversion of fructose to 2,5-dimethyltetrahydrofuran.

Matthew R Grochowski, Weiran Yang, Ayusman Sen

Index: Chemistry 18(39) , 12363-71, (2012)

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Abstract

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 RhX(3) (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 H(2)O) in the initial step of the reaction, and as a reducing agent for the conjugated carbinol group in a subsequent step. I(2) 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.Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.