Eschenmoser sulfide contraction

The Eschenmoser sulfide contraction is an organic reaction first described by Albert Eschenmoser for the synthesis of 1,3-dicarbonyl compounds from a thioester.[1][2][3] The method requires a base and a tertiary phosphine. The method is of some relevance to organic chemistry and has been notably applied in the vitamin B12 total synthesis.

A base abstracts the labile hydrogen atom in the thioester, a sulfide anion is formed through an episulfide intermediate which is removed by the phosphine.[4]

Scope

The Eschenmoser sulfide contraction method has been employed in a number of total synthesis efforts, like that of fuligocandin A and B,[5] cocaine,[6] diplodialide A [7] and isoretronecanol [8]

An example of general synthetic utility is the synthesis of novel carbapenems [9]

References
  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, Date: May 1969, Pages: 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, Pages: 710-734 M. Roth, P. Dubs, E. Götschi, A. Eschenmoser doi:10.1002/hlca.19710540229
  4. Loeliger, P.; Flückiger, E. (1976). "Sulfide Contraction via Alkylative Coupling: 3-Methyl-2,4-Hepthanedione". Organic Syntheses. 55: 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. J. Org. Chem., 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 J. Org. Chem., 1978, 43 (24), pp 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, Pages 2187-2190 Osamu Sakurai, Tsuyoshi Ogiku, Masami Takahashi, Hiroshi Horikawa, Tameo Iwasaki doi:10.1016/S0040-4039(00)76792-X
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