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Synthesis 1972; 1972(6): 285-302
DOI: 10.1055/s-1972-21869
review
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Organic Syntheses Using Lead (IV) Acetate Azides

Erich ZBIRAL*
  • *Organisch-chemisches Institut der Universität Wien (Vienna), Austria
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Publication Date:
12 March 2002 (online)

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This review encompasses a number of syntheses involving the reaction of a wide variety of olefins with lead(IV) acetate azides, Pb(OAc)4-n(N3)n the existence of which was first reported in 1969. Depending on the olefin used, the products of such reactions may be vic-diazido compounds, vic-acetoxyazido compounds (occasionally also gem-diazido or gem-acetoxyazido compounds), α-azidocarbonyl compounds, or ketonitriles. Reactions involving steroidal olefins have shown particular synthetic promise. Bridged olefins such as camphene, norbornene, benzonorbornadiene, and dibenzobarrelene undergo structural rearrangements typical for these classes of compounds in polar reactions. Lead(IV) acetate azides, Pb(OAc)4-n(N3)n also undergo characteristic reactions with C≡C triple bonds. In the case of reactions carried out at reduced temperature (-20°), the reaction products in nearly all cases contain the azido group at the same carbon atom at which the positive moiety is attached in other polar reactions. At room temperature, radical substitution reactions also appear to occur. In addition to the reactions of lead(IV) acetate azides, some reactions of olefins with the related system are reported in the last section of the review. 1. Synthesis of Pb(OAc)4-n(N3)n from Lead(IV)-acetate and Trimethylsilyl Azide 2. Reactions of Pb(OAc)4-n(N3)n with C=C Double Bonds in Simple Molecules 2.1. Reactions with Stilbenes and Other Alkenes 2.2. Reactions with Styrene Derivatives 2.3. Reactions with Bridged Olefins 3. Reactions of Pb(OAc)4-n(N3)n with Triple Bonds 4. Reactions of Steroids with Pb(OAc)4-n(N3)n 4.1. General 4.2. Elucidation of the Fragmentation Reaction 4.3. Formation of α-Azidocarbonylsteroids 4.4. Interpretation of Results 5. Possible Radical Reactions with Pb(OAc)4-n(N3)n 6. Conclusion 7. Appendix. Reactions with the System C6H5J(OAc)2/(CH3)3SiN3

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