Facile synthesis of cis-2-Alkyl-3-trialkylsilyloxycycloalkanones via the non-aldol aldol rearrangement of 2,3-epoxycycloalkanols.
Silyl triflate-promoted rearrangement of cis-2,3-epoxycycloalkanols A, prepared by epoxidation of the cyclic allylic alcohol and then silylation, afforded good yields ( approximately 70-75%) of the cis-2-alkyl-3-silyloxycycloalkanones B, presumably via the intermediates C and D, even with quite large alpha-substituents, e.g., tert-butyl. Finally, it has been shown that the stereochemistry of the epoxy alcohol is crucial as one would expect from the mechanism.
Jung
Michael E
ME
Department of Chemistry and Biochemistry, University of California, Los Angeles, 405 Hilgard Avenue, Los Angeles, California 90095, USA. jung@chem.ucla.edu
Allen
Damian A
DA
D004852:Epoxy Compounds / Q000737:chemistry*; D007659:Ketones / Q000138:chemical synthesis* / Q000737:chemistry; D008968:Molecular Conformation; D012821:Silanes / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
D004852:Epoxy Compounds; D007659:Ketones; D012821:Silanes