Ferrier rearrangement

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The Ferrier rearrangement is a name reaction in organic chemistry . In 1914, the German Nobel Laureate in Chemistry, Emil Fischer (1852-1919), reported on this reaction for the first time, and Robert J. Ferrier published further publications from 1979 onwards . The rearrangement takes place in the presence of a Lewis acid on unsaturated compounds. This rearrangement reaction is often referred to as type II of the Ferrier rearrangement.

Overview reaction

In the Ferrier rearrangement, exocyclic enol ethers are converted to substituted cyclohexanones using mercury (II) salts. This rearrangement got synthetic relevance due to the following features:

  • the synthesis of chiral , highly substituted cyclohexanone derivatives is possible
  • in most transformations an isolated diastereomer can be synthesized in high yield
  • the Lewis acid (e.g. HgCl 2 ) can be used in catalytic amounts so that complex products with acid-sensitive groups can be synthesized

Reaction mechanism

In the first step of the proposed reaction mechanism of type II the Ferrier rearrangement, a regiospecific mercuration takes place on enol ether 1 in order to produce a ketoaldehyde 2 as an intermediate. In addition to mercury (II) chloride, other mercury (II) salts can also be used. A subsequent intramolecular cyclization produces the corresponding cyclohexanone 3 .

application

Noritaka Chida used type II of the Ferrier rearrangement to produce the sesquiterpene paniculide A from D-glucose . In addition, type II was also used by Seiichiro Ogawa in the synthesis of the natural product (+) - lycoricidin .

See also

Individual evidence

  1. ↑ a b c d e László Kürti , Barbara Czakó: Strategic applications of named reactions in organic synthesis: background and detailed mechanisms . Elsevier Academic Press, Amsterdam 2005, ISBN 0-12-429785-4 , pp. 168-169 .
  2. ^ A b Robert J. Ferrier: Unsaturated carbohydrates. Part 21. A carbocyclic ring closure of a hex-5-enopyranoside derivative . In: Journal of the Chemical Society, Perkin Transactions 1 . 1979, p. 1455 , doi : 10.1039 / p19790001455 .
  3. ^ Robert J. Ferrier, Sydney. Middleton: The conversion of carbohydrate derivatives into functionalized cyclohexanes and cyclopentanes . In: Chemical Reviews . tape 93 , no. 8 December 1993, pp. 2779-2831 , doi : 10.1021 / cr00024a008 .
  4. ↑ Noritaka Chida, Masami Ohtsuka, Katsuyuki Ogura, Seiichiro Ogawa: Synthesis of Optically Active Substituted Cyclohexenones from Carbohydrates by Catalytic Ferrier Rearrangement . In: Bulletin of the Chemical Society of Japan . tape 64 , no. 7 , 1991, pp. 2118-2121 , doi : 10.1246 / bcsj.64.2118 .
  5. ^ RJ Ferrier, N. Prasad: Unsaturated carbohydrates. Part IX. Synthesis of 2,3-dideoxy-α-D -erythro-hex-2-enopyranosides from tri-O-acetyl-D -glucal . In: J. Chem. Soc. C . tape 0 , no. 4 , 1969, p. 570-575 , doi : 10.1039 / J39690000570 .
  6. ^ RD (Gus) Guthrie, Robert W. Irvine: Allylic substitutions in tri-O-acetyl-glycals and related compounds . In: Carbohydrate Research . tape 82 , no. 2 , 1980, p. 207-224 , doi : 10.1016 / S0008-6215 (00) 85698-0 .
  7. ^ Antonio S. Machado, Didier Dubreuil, Jeannine Cleophax, Stephane D. Gero, Noel F. Thomas: Expedient syntheses of inososes from carbohydrates: conformational and stereoelectronic aspects of the Ferrier reaction . In: Carbohydrate Research . tape 233 , 1992, pp. C5-C8 , doi : 10.1016 / S0008-6215 (00) 90945-5 .
  8. ↑ Noriaki Yamauchi, Takumi Terachi, Tadashi Eguchi, Katsumi Kakinuma: Mechanistic and stereochemical studies on Ferrier reaction by means of chirally deuterated glucose . In: Tetrahedron . tape 50 , no. 14 , 1994, pp. 4125-4136 , doi : 10.1016 / S0040-4020 (01) 86708-9 .
  9. ↑ Didier Dubreuil, Jeannine Cleophax, Mauro Vieira de Almeida, Catherine Verre-Sebrié, Jérôme Liaigre: Stereoselective synthesis of 6-deoxy and 3,6-dideoxy-D-myo-inositol precursors of deoxy-myo-inositol phosphate analogues from D- galactose . In: Tetrahedron . tape 53 , no. 49 , December 1997, p. 16747-16766 , doi : 10.1016 / S0040-4020 (97) 10101-6 .
  10. ↑ Leo A. Paquette, Margaret J. Kinney, Uta Dullweber: Practical Synthesis of Spirocyclic Bis-C, C-glycosides. Mechanistic Models in Explanation of Rearrangement Stereoselectivity and the Bifurcation of Reaction Pathways . In: The Journal of Organic Chemistry . tape 62 , no. 6 , 1997, pp. 1713-1722 , doi : 10.1021 / jo962020i .
  11. ↑ Robert J. Ferrier: Substitution-with-Allylic-Rearrangement Reactions of Glycal Derivatives . In: Topics in Current Chemistry . Springer Berlin Heidelberg, Berlin, Heidelberg 2001, ISBN 978-3-540-41383-7 , pp. 153-175 .
  12. ↑ Seiji Amano, Noriaki Takemura, Masami Ohtsuka, Seiichiro Ogawa, Noritaka Chida: Total synthesis of paniculide A from d-glucose . In: Tetrahedron . tape 55 , no. 13 , 1999, p. 3855-3870 , doi : 10.1016 / S0040-4020 (99) 00096-4 .
  13. ↑ Noritaka Chida, Masami Ohtsuka, Seiichiro Ogawa: Total synthesis of (+) - lycoricidine and its 2-epimer from D-glucose . In: The Journal of Organic Chemistry . tape 58 , no. 16 , 1993, pp. 4441-4447 , doi : 10.1021 / jo00068a045 .