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Triphenylphosphine reduction of saturated endoperoxides.

ABSTRACT: 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.

SUBMITTER: Erden I

PROVIDER: S-EPMC2760492 | biostudies-literature | 2009 Sep

REPOSITORIES: biostudies-literature

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Triphenylphosphine reduction of saturated endoperoxides.

Erden Ihsan I Gärtner Christian C Azimi M Saeed MS

Organic letters 20090901 17

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 att ...[more]

PMID: 19655767

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