TY - JOUR
T1 - Mechanistic study of a one-step catalytic conversion of fructose to 2,5-dimethyltetrahydrofuran
AU - Grochowski, Matthew R.
AU - Yang, Weiran
AU - Sen, Ayusman
PY - 2012/9/24
Y1 - 2012/9/24
N2 - 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 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.
AB - 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 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.
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U2 - 10.1002/chem.201201522
DO - 10.1002/chem.201201522
M3 - Article
C2 - 22915231
AN - SCOPUS:84866427424
SN - 0947-6539
VL - 18
SP - 12363
EP - 12371
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 39
ER -