6533b857fe1ef96bd12b391e

RESEARCH PRODUCT

Proton Acid-induced Rearrangements of α-Alkynylestradiol Methyl Ethers

Thomas SchallUlf Pindur

subject

chemistry.chemical_compoundAcid catalysisReaction mechanismchemistryProtonDeuteriumOrganic ChemistryOrganic chemistrySulfuric acidEtherPhysical and Theoretical ChemistryEnoneCatalysis

description

When subjected to proton catalysis, the α-alkynylestradiol methyl ethers 1a and 1b furnish the Rupe or Meyer-Schuster rearrangement products 2, 4, and 5a. In the presence of sulfuric acid, α-ethynylestradiol 3-methyl ether (1a) is converted into the D-homosteroid 3a. The use of deuterated acids gives rise to the formation of the corresponding deuterated steroids 2b, 2c, 3b, and 5b. Some mechanistic implications of these results are also discussed.

https://doi.org/10.1002/jlac.1993199301176