Abstract
Rearrangements which lead to the formation of compounds with a free carbocyclic spiro linkage are reviewed. The reactions are classified as proceeding via acid-catalyzed, thermal, photolytic, or miscellaneous rearrangements. 1. Acid-Catalyzed Rearrangements 1.1. Pinacols 1.2. Amine Deaminations 1.3. Alcohols and Cyclic Acetals 1.4. Oxiranes 1.5. Unsaturated Substrates 2. Thermal Rearrangements 2.1. Oxiranes 2.2. 1-Vinylcyclopropanols 2.3. α,β-Epoxyketones 2.4. α-Diazocycloalkanones - Wolff Rearrangement to Ketenes 2.5. Acetate Pyrolysis 2.6. Reorganizations of Olefinic Substrates 2.7. Pentaoxyphosphoranes 3. Photolytic Rearrangements 3.1. Cyclic Cross-Conjugated Dienones 3.2. Cycloalkenones 3.3. 2-Methylenebicyclo[3.1.0]-3-hexene Isomerizations 3.4. α,β-Epoxyketones 3.5. Assorted Substrates 3.6. Photostereoisomerizations 4. Miscellaneous Rearrangements

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