Triphenylphosphine reduction of saturated endoperoxides.
Triphenylphosphine reduction of saturated endoperoxides derived from 6,6-dimethylfulvene and spiro[2.4]hepta-4,6-diene in the presence of nucleophiles results in the formation of products that mainly stem from deoxygenation followed by carbocation formation. Nucleophilic attack by solvent proceeds by an S(N)1 like mechanism; allyl shifts and cyclopropylcarbinyl-cyclobutyl rearrangements also occur. With the systems lacking carbocation-stabilizing groups, the deoxygenation step is preceded by attack of H(2)O at the phosphorus.
Erden
Ihsan
I
San Francisco State University, Department of Chemistry and Biochemistry, 1600 Holloway Avenue, San Francisco, California 94132, USA. ierden@sfsu.edu
Gärtner
Christian
C
Azimi
M Saeed
MS
D000085:Acetates / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D015394:Molecular Structure; D009943:Organophosphorus Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D010545:Peroxides / Q000737:chemistry*
D000085:Acetates; D009943:Organophosphorus Compounds; D010545:Peroxides; C061896:triphenylphosphine