Sulfoxide and Selenoxide syn-Eliminations

Preparation of α-Phenylseleno Carbonyl Compounds

Reich Acc. Chem. Res, 1979, 12, 22.

  
  

Sensitive α,β-Unsaturated Carbonyl Compounds Prepared by Selenoxide Elimination

Reich, Renga, Reich J. Am. Chem. Soc. 1975, 97, 5434

  

Male Dried Bean Beetle Sex Pheromone: Kocienski, P.; Cernogliaro, G.; Feldstein, G. J. Org. Chem. 1977, 42, 353

  

  Although PhSe groups are usually introduced α to carbonyl groups by reaction of a lithium enolate with PhSeCl, PhSeBr or PhSeSePh, sometimes problems with proton transfer during the selenation can lead to bisselenated byproducts. First converting carbonyl compound to an enol silyl ether, and then reaction with PhSeCl often leads to cleaner products.

Akuammicine: Bonjoch, J.; Sole, D.; Garcia-Rubio, S.; Bosch, J. J. Am. Chem. Soc. 1997, 119, 7230

  
  

  Use of enone as directing/protecting group. Quadrone Danishefsky, S.; Vaughan, K.; Gadwood, R. C.; Tsuzuki, K. J. Am. Chem. Soc. 1981, 103, 4136.

  

  Selenoxide Elimination - Synthesis of Milbemycin D: M. T. Crimmins, et al. J. Am. Chem. Soc. 1996, 118, 7513

  

  Seleninylation of Enolates for Oxidation-Sensitive Substrates: Breynolide: Smith, A. B. III; Empfield, J. R.; Rivero, R. A.; Vaccaro, H. A.J. Am. Chem. Soc., 1991, 113, 4037.

  

Conversion of Epoxides to Allyl Alcohols

Dihydrobenzenediols: Schlessinger J. Org. Chem. 1981, 46, 5253

  

Synthesis of Chorismic Acid Analog: Mattia, Ganem J. Org. Chem. 1994, 59, 720.

  

Fürst-Plattner Rule (Trans Diaxial Effect)

  Cyclohexene epoxides undergo ring opening with nucleophiles to give diaxial products. These effects fundamentally arise from the inherent preference of cyclohexanes for the chair over the twist-boat conformation (Fürst, A.; Plattner, P. A. Helv. Chim. Acta 1949, 32, 275).

Aloperine (iso): Brosius, A. D.; Overman, L. E. J. Org. Chem. 1997, 62, 440

  

Introduction of S and Se Functions as Appendages

Hemibrevetoxin - using γ-Phenylseleno Wittig Reagent: Kadota, Yamamoto J. Org. Chem. 1998, 63, 6597.

  
  

Antillatoxin Isomer: Yomakawa, Shiori J. Org. Chem. 1998, 63, 8638. DOI