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Mechanistic Study of a One‐Step Catalytic Conversion of Fructose to 2,5‐Dimethyltetrahydrofuran
Author(s) -
Grochowski Matthew R.,
Yang Weiran,
Sen Ayusman
Publication year - 2012
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201201522
Subject(s) - chemistry , catalysis , rhodium , fructose , reducing agent , metal , conjugated system , combinatorial chemistry , hydrogen , organic chemistry , polymer
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 CO and CC 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.