Eschenmoserova sulfidová kontrakce

Eschenmoserova sulfidová kontrakce je organická reakce vytvářející 1,3-dikarbonylové sloučeniny z thioesterů za přítomnosti terciárních fosfinů v zásaditém prostředí; objevil ji Albert Eschenmoser.^[1]^[2]^[3]

Uplatněna byla tato reakce mimo jiné při totální syntéze vitaminu B12.

Mechanimus

Zásada odštěpí vodíkový atom thioesteru, poté se vytvoří sulfidový anion přes episulfidový meziprodukt, a působením fosfinu vznikne konečný produkt.^[4]

Rozsah

Eschenmoserova sulfidová kontrakce byla zahrnuta do několika totálních syntéz, například fuligokandinu A a B,^[5] kokainu,^[6] diplodialidu A^[7] a isoretronekanolu.^[8] Využít ji lze také k přípravě karbapenemů. ^[9]

Reference

V tomto článku byl použit překlad textu z článku Eschenmoser sulfide contraction na anglické Wikipedii.

↑ Organic syntheses based on name reactions, Volume 22 2002 Alfred Hassner,C. Stumer
↑ A New Type of Corrin Synthesis Angewandte Chemie International Edition in English Volume 8, Issue 5, May 1969, 343-348 Yasuji Yamada, D. Miljkovic, P. Wehrli, B. Golding, P. Löliger, R. Keese, K. Müller, A. Eschenmoser DOI:10.1002/anie.196903431
↑ Sulfidkontraktion via alkylative Kupplung: Eine methode zur darstellung von -dicarbonylderivaten. Über synthetische methoden, 1. Mitteilung Helvetica Chimica Acta Volume 54, Issue 2, Date: 1971, 710-734 M. Roth, P. Dubs, E. Götschi, A. Eschenmoser DOI:10.1002/hlca.19710540229
↑ P. Loeliger; E. Flückiger. Sulfide Contraction via Alkylative Coupling: 3-Methyl-2,4-Hepthanedione. Organic Syntheses. 1976, s. 127. DOI 10.15227/orgsyn.055.0127.
↑ One-Pot Eschenmoser Episulfide Contractions in DMSO: Applications to the Synthesis of Fuligocandins A and B and a Number of Vinylogous Amides Birgitta Pettersson, Vedran Hasimbegovic, Jan Bergman The Journal of Organic Chemistry 2011 76 (6), 1554-1561 DOI:10.1021/jo101864n
↑ Enantiospecific Synthesis of Natural (−)-Cocaine and Unnatural (+)-Cocaine from d- and l-Glutamic Acid Ronghui Lin, Josep Castells, and, Henry Rapoport The Journal of Organic Chemistry 1998 63 (12), 4069-4078 DOI:10.1021/jo980153t
↑ Macrocyclic lactone formation through sulfide contraction. Synthesis of (±)-diplodialide A Robert E. Ireland, Frank R. Brown Jr. The Journal of Organic Chemistry, 1980, 45 (10), pp 1868–1880 DOI:10.1021/jo01298a022
↑ New approaches to the pyrrolizidine ring system: total synthesis of (±)-isoretronecanol and (±)-trachelanthamidine Harold W. Pinnick, Yeong-Ho Chang The Journal of Organic Chemistry, 1978, 43 (24), 4662–4663 DOI:10.1021/jo00418a031
↑ A new synthetic method of 1β-methylcarbapenems utilizing the eschenmoser sulfide contraction Tetrahedron Letters, Volume 35, Issue 14, 4 April 1994, 2187-2190 Osamu Sakurai, Tsuyoshi Ogiku, Masami Takahashi, Hiroshi Horikawa, Tameo Iwasaki DOI:10.1016/S0040-4039(00)76792-X

[1] Organic syntheses based on name reactions, Volume 22 2002 Alfred Hassner,C. Stumer

[2] A New Type of Corrin Synthesis Angewandte Chemie International Edition in English Volume 8, Issue 5, May 1969, 343-348 Yasuji Yamada, D. Miljkovic, P. Wehrli, B. Golding, P. Löliger, R. Keese, K. Müller, A. Eschenmoser DOI:10.1002/anie.196903431

[3] Sulfidkontraktion via alkylative Kupplung: Eine methode zur darstellung von -dicarbonylderivaten. Über synthetische methoden, 1. Mitteilung Helvetica Chimica Acta Volume 54, Issue 2, Date: 1971, 710-734 M. Roth, P. Dubs, E. Götschi, A. Eschenmoser DOI:10.1002/hlca.19710540229

[4] P. Loeliger; E. Flückiger. Sulfide Contraction via Alkylative Coupling: 3-Methyl-2,4-Hepthanedione. Organic Syntheses. 1976, s. 127. DOI 10.15227/orgsyn.055.0127.

[5] One-Pot Eschenmoser Episulfide Contractions in DMSO: Applications to the Synthesis of Fuligocandins A and B and a Number of Vinylogous Amides Birgitta Pettersson, Vedran Hasimbegovic, Jan Bergman The Journal of Organic Chemistry 2011 76 (6), 1554-1561 DOI:10.1021/jo101864n

[6] Enantiospecific Synthesis of Natural (−)-Cocaine and Unnatural (+)-Cocaine from d- and l-Glutamic Acid Ronghui Lin, Josep Castells, and, Henry Rapoport The Journal of Organic Chemistry 1998 63 (12), 4069-4078 DOI:10.1021/jo980153t

[7] Macrocyclic lactone formation through sulfide contraction. Synthesis of (±)-diplodialide A Robert E. Ireland, Frank R. Brown Jr. The Journal of Organic Chemistry, 1980, 45 (10), pp 1868–1880 DOI:10.1021/jo01298a022

[8] New approaches to the pyrrolizidine ring system: total synthesis of (±)-isoretronecanol and (±)-trachelanthamidine Harold W. Pinnick, Yeong-Ho Chang The Journal of Organic Chemistry, 1978, 43 (24), 4662–4663 DOI:10.1021/jo00418a031

[9] A new synthetic method of 1β-methylcarbapenems utilizing the eschenmoser sulfide contraction Tetrahedron Letters, Volume 35, Issue 14, 4 April 1994, 2187-2190 Osamu Sakurai, Tsuyoshi Ogiku, Masami Takahashi, Hiroshi Horikawa, Tameo Iwasaki DOI:10.1016/S0040-4039(00)76792-X

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