Oxonia-cope prins cyclizations: a facile method for the synthesis of tetrahydropyranones bearing quaternary centers.
A new cationic cascade reaction has been developed that produces 4-tetrahydropyranones in good yield. The reaction is based on the facile 2-oxonia Cope rearrangement of allyl-substituted oxocarbenium ions. In the presence of a more nucleophilic silyl enol ether, such systems rearrange and cyclize to produce tetrahydropyranones. The substrates were prepared by silyl ketene acetal addition to ketenes. The rearrangement is compatible with tetrasubstituted silyl enol ethers, which result in the diastereoselective introduction of quaternary centers at the C3 position of the tetrahydropyran ring. The oxonia-Cope Prins rearrangement is a versatile new route to tetrahydropyrans.
Dalgard
Jackline E
JE
Department of Chemistry, University of California, Irvine, Irvine, California 92697-2025, USA.
Rychnovsky
Scott D
SD
D000085:Acetates / Q000737:chemistry*; D001685:Biological Factors / Q000138:chemical synthesis; D003500:Cyclization; D004164:Diphosphonates / Q000737:chemistry*; D006861:Hydrogen Peroxide / Q000737:chemistry*; D011714:Pyrans / Q000138:chemical synthesis*; D013237:Stereoisomerism
D000085:Acetates; D001685:Biological Factors; D004164:Diphosphonates; C118890:Oxonia Active; D011714:Pyrans; D006861:Hydrogen Peroxide