Achmatowicz reaction

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Achmatowicz reaction
Named afterOsman Achmatowicz Jr.
Reaction type Rearrangement reaction
Identifiers
RSC ontology ID RXNO:0000233

The Achmatowicz reaction, also known as the Achmatowicz rearrangement, is an organic synthesis in which a furan is converted to a dihydropyran. In the original publication by the Polish chemist Osman Achmatowicz Jr. (b. 20 December 1931 in Vilnius) in 1971 [1] furfuryl alcohol is reacted with bromine in methanol to 2,5-dimethoxy-2,5-dihydrofuran which rearranges to the dihydropyran with dilute sulfuric acid. Additional reaction steps, alcohol protection with methyl orthoformate and boron trifluoride) and then ketone reduction with sodium borohydride produce an intermediate from which many monosaccharides can be synthesised.

The Achmatowicz reaction.svg

The Achmatowicz protocol has been used in total synthesis, including those of desoxoprosophylline, [2] pyrenophorin [3] [4] Recently it has been used in diversity oriented synthesis [5] [6]

AchmatowiczBurke2006.svg

and in enantiomeric scaffolding. [7] [8]

AchmatowiczReactionCoombs2008.svg

References

  1. ↑ Achmatowicz, O.; Bukowski, P.; Szechner, B.; Zwierzchowska, Z.; Zamojski, A. (1971-01-01). "Synthesis of methyl 2,3-dideoxy-DL-alk-2-enopyranosides from furan compounds: A general approach to the total synthesis of monosaccharides". Tetrahedron. 27 (10): 1973–1996. doi:10.1016/S0040-4020(01)98229-8. ISSN   0040-4020.
  2. ↑ Yang, Cui-Fen; Xu, Yi-Ming; Liao, Li-Xin; Zhou, Wei-Shan (1998-12-10). "Asymmetric total synthesis of (+)-desoxoprosophylline". Tetrahedron Letters. 39 (50): 9227–9228. doi:10.1016/S0040-4039(98)02129-7. ISSN   0040-4039.
  3. ↑ Kobayashi, Yuichi; Nakano, Miwa; Kumar, G. Biju; Kishihara, Kiyonobu (1998-10-01). "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". The Journal of Organic Chemistry. 63 (21): 7505–7515. doi:10.1021/jo980942a. ISSN   0022-3263. PMID   11672404.
  4. ↑ Zhang, Yongqiang; Liebeskind, Lanny S. (2006-01-01). "Organometallic Enantiomeric Scaffolding: Organometallic Chirons. Total Synthesis of (−)-Bao Gong Teng A by a Molybdenum-Mediated [5+2] Cycloaddition". Journal of the American Chemical Society. 128 (2): 465–472. doi:10.1021/ja055623x. ISSN   0002-7863. PMID   16402833.
  5. ↑ Reagents: NBS, PPTS, for macrobeads see: solid-phase synthesis
  6. ↑ Burke, Martin D.; Berger, Eric M.; Schreiber, Stuart L. (2004-11-01). "A Synthesis Strategy Yielding Skeletally Diverse Small Molecules Combinatorially". Journal of the American Chemical Society. 126 (43): 14095–14104. doi:10.1021/ja0457415. ISSN   0002-7863. PMID   15506774.
  7. ↑ Coombs, Thomas C.; Lee; Wong, Heilam; Armstrong, Matthew; Cheng, Bo; Chen, Wenyong; Moretto, Alessandro F.; Liebeskind, Lanny S. (2008-02-01). "Practical, Scalable, High-Throughput Approaches to η3-Pyranyl and η3-Pyridinyl Organometallic Enantiomeric Scaffolds Using the Achmatowicz Reaction". The Journal of Organic Chemistry. 73 (3): 882–888. doi:10.1021/jo702006z. ISSN   0022-3263. PMC   2652699 . PMID   18171075.
  8. ↑ Reagents: benzyl chloroformate protects amine as Cbz group, Achmatowitz reaction with m-CPBA, complexation with a molybdenum compound, Cp is cyclopentadienyl anion
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