Achmatowicz reaction
The Achmatowicz reaction, or Achmatowicz rearrangement , is an organic name reaction in which a furan is converted into a dihydropyran .
history
The formation of furans from mono- and polysaccharides under the action of mineral acids was already known in the 19th century. Already in 1832 Johann Wolfgang Döbereiner was able to produce the poisonous oil furfural by heating sugars with sulfuric acid and manganese (IV) oxide . In 1970, K. Tsuji and I. Fujimaki were able to obtain 2-methyl-3-formylfuran by heating a streptose derivative at pH 2-4.
In 1971, at the Institute of Organic Chemistry at the Polish Academy of Sciences , O. Achmatowicz Jr. , P. Bukowski, B. Szechner, Z. Zwierzchowska and A. Zamojski did the reverse reaction for the production of sugars from furan derivatives, in particular the production of Monosaccharides developed from simple furans. Here, a is furfuryl alcohol with bromine in methanol, allowed to react and eventually forms a stereoisomer mixture of cis - and trans -isomers of 2,5-dimethoxy-2,5-dihydrofuranderivats. It then reacts with dilute sulfuric acid , splitting the acetal to form a dicarbonyl component, which immediately cyclizes to a dihydropyran derivative .
application
Further steps in the reaction are the protection of the alcohol with trimethyl orthoformate and boron trifluoride , followed by the reduction of the formed ketones with sodium borohydride , resulting in an intermediate product from which many monosaccharides can be synthesized.
Basic reaction
The Achmatowitz reaction has been used for total synthesis , including that of deoxoprosophylline and pyrenophorine.
The process is also used in divergent synthesis .
Achmatowicz-Burke 2006
Achmatowicz reaction 2008
Remarks
Individual evidence
- ↑ JW Döbereiner: About the medical and chemical application and the advantageous presentation of formic acid. In: Annals of Pharmacy. Volume 3, 1832, p. 141.
- ↑ K. Tsuji, I. Fujimaki: Formation of 2-methyl-3-formylfuran from reduced streptomycin. In: Tetrahedron Letters. Volume 48, October 1970, p. 4229.
- ↑ O. Achmatowicz, P. Bukowski, B. Szechner, Z. Zwierzchowska and A. Zamojski: Synthesis of methyl 2,3-dideoxy-alk-2-enopyranosides from furan compounds: A general approach to the total synthesis of monosaccharides . In: Tetrahedron . tape 27 , no. 10 , 1971, p. 1973-1996 (English). doi : 10.1016 / S0040-4020 (01) 98229-8 .
- ↑ Cui-Fen Yang, Yi-Ming Xu, Li-Xin Liao and Wei-Shan Zhou: Asymmetric total synthesis of (+) - desoxoprosophylline . In: Tetrahedron Letters . tape 39 , no. 50 , December 10, 1998, pp. 9227-9228 (English). doi : 10.1016 / S0040-4039 (98) 02129-7 .
- ↑ Kobayashi, Y .; Nakano, M .; Kumar, GB and Kishihara, K .: Efficient Conditions for Conversion of 2-Substituted Furans into 4-Oxygenated 2-Enoic Acids and Its Application to Synthesis of (+) - Aspicilin, (+) - Patulolide A, and ( -) - Pyrenophorin . In: J. Org. Chem. Band 63 , no. 21 , 1998, pp. 7505-7515 (English). doi : 10.1021 / jo980942a .
- ^ Yongqiang Zhang and Lanny S. Liebeskind: Organometallic Enantiomeric Scaffolding: Organometallic Chirons. Total Synthesis of ( -) - Bao Gong Teng A by a Molybdenum-Mediated [5 + 2] Cycloaddition . In: J. Am. Chem. Soc. tape 128 , 2006, p. 465-472 . doi : 10.1021 / ja055623x .
- ↑ Martin D. Burke, Eric M. Berger and Stuart L. Schreiber: A Synthesis Strategy Yielding Skeletally Diverse Small Molecules Combinatorially . In: J. Am. Chem. Soc. tape 126 , no. 43 , 2004, p. 14095-14104 (English). doi : 10.1021 / ja0457415 .
