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Synthesis 1987; 1987(9): 749-789
DOI: 10.1055/s-1987-28074
review
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Addition and Cycloaddition Reactions of Tetracyanoethylene (TCNE) in Organic Chemistry

Alexander J. Fatiadi*
  • *Center for Analytical Chemistry, National Bureau of Standards, Gaithersburg, Maryland 20899, U. S. A.
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Publication Date:
12 September 2002 (online)

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The present review is mainly concerned with selected addition and cycloaddition reactions of tetracyanoethylene that have use or potential use in organic synthesis. Emphasis has been laid on recent developments in [2 + 2]cycloaddition, the Diels-Alder reaction, the ene reaction, and higher-order cycloaddition of TCNE to carbocyclic and heterocyclic substrates. Also, the mechanistic aspects, and recent developments in thermal and photocycloaddition reactions, are discussed. 1. Introduction 1.1. General Considerations 2. Scope of the Review 3. The Diels-Alder Reaction and Related [4 + 2]Cycloaddition (Mechanism) 3.1. Involvement of Radical-Ion Pairs in [4 + 2]Cycloadditions 4. The Homo-Diels-Alder Reaction 4.1. Reaction of Hexamethyl (Dewar Benzene) with TCNE 4.2. Reaction of Benzvalene with TCNE 5. The Alder Ene Reaction 6. Thermal [2 + 2]Cycloadditions Using TCNE 6.1.The Huisgen Mechanism 7. Cycloaddition Reactions of Cyclopropyl Derivatives with TCNE 7.1. Reaction of Alkenylcyclopropanes with TCNE 7.2. Reaction of Diphenylcyclopropanes with TCNE 7.3. Dienophilic and Dipolar Additions to Vinylcyclopropanes 7.4. Vinylcyclobutane-Cyclohexene Rearrangement 7.5. Novel Addition of TCNE to Dicyclopropylfulvene 7.6. Reaction of Cyclopropene Hydrocarbons with TCNE 7.7. Novel Cycloaddition of Cyclopropanes with TCNE. Synthesis of Larger-Ring Alkenes and Dienes 7.8. Cycloaddition of TCNE to Spiro-1,3-Dienes in the Presence of Small-Ring Ethers 7.9. Cycloaddition of TCNE to Cyelopropylallenes 8. Cycloaddition of Conjugated Dienes, Allenes, and Polyenes with TCNE 9. Stereoselective Additon of TCNE to Exocyclic Dienes 10. Reaction of Cyclic dienes, Trienes, and Tetraenes with TCNE, e.g., [4]Annulenes, Fulvenes, Bullvalenes, and Cyclooctatetraenes 11. Reaction of Cyclophanes with TCNE 12. C ycloaddition of TCNE with Aromatic Hydrocarbons 13. Photochemical Reactions in the Presence of TCNE 14. Reaction of Heterocyclics with TCNE 14.1. Reaction of Ring-Oxygen Heterocyclics with TCNE 14.2. Reaction of Ring-Nitrogen Heterocyclics with TCNE 14.3. Reaction of Mesoionic Compounds with TCNE 14.4. Additional Reactions of Heterocyclics with TCNE 15. Miscellaneous Addition and Cycloaddition Reactions Involving TCNE