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Triphenylphosphine Reduction of Saturated Endoperoxides

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journal contribution
posted on 03.09.2009, 00:00 by Ihsan Erden, Christian Gärtner, M. Saeed Azimi
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 SN1 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 H2O at the phosphorus.