The chapter presents an overview of the origins of carbene chemistry. The structure and reactivity in the case of carbenes is presented and the complex nature of the rearrangements of arylcarbenes is analyzed. A description of the use of frozen organic matrices to study their chemistry is also presented. In addition, the matrix chemistry of arylcarbenes is explained in terms of a thermal singlet-triplet equilibration in which the relative amounts of singlet and triplet chemistry is determined. The chemistry and synthesis of allenes are then reviewed. The syntheses for allenes are done by elimination reactions. The reactions discussed include metalation, photo addition reactions, thermal rearrangements, cycloadditions, and addition reactions. The functionalized allenes presented are silylallenes, allene oxides, hydroxyallenes, silyloxyallenes, acetoxyallenes, and alkoxyallenes. The preparation and cyclization of allenic amides and amines to the corresponding pyrrolidines of piperidines respectively by the action of palladium (II) chloride and cupric chloride are illustrated. Finally, the carbonyl derivatives of allenes, allenic nitriles, allenic sulphones and allenic boronates are discussed.
|Title of host publication||Second Supplements to the 2nd Edition of Rodd's Chemistry of Carbon Compounds|
|Subtitle of host publication||A Modern Comprehensive Treatise|
|Number of pages||72|
|Publication status||Published - 1991|