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.
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
