References
- Gerlach , G. 1875 . Justus Liebigs Ann. Chem. , 178 : 80 In general, the allylic (3,3) thiocyanate isomerizations are believed to pass through a cyclic intermediate in which the thiocyanate moiety is not detached from the alkyl group. Saturated or allylic (1,3) thiocyanate isomerizations have a higher energy of activation and are believed to occur by ionization and recombination. For a review of thiocyanate isomerizations see
- Billeter , O. 1875 . Chem. Ber. , 8 : 462
- Mumm , O. and Richter , H. 1940 . Chem. Ber. , 73 : 843
- Iliceto , A. , Fava , A. and Mazzucato , U. 1960 . Tetrahedron Lett. , 11 : 27
- Iliceto , A. and Gaggia , G. 1960 . Gazz. Chim. Ital. , 90 : 262
- Smith , P. A. S. and Emerson , D. W. 1960 . J. Am. Chem. Soc. , 82 : 3076
- Emerson , D. W. 1971 . J. Chem. Educ. , 48 : 81
- Kloft , M. and Hoppe , D. 1976 . Justus Liebigs Ann. Chem. , : 1997 D. Hoppe, Justus Liebigs Ann. Chem., 2185 (1976); D. Hoppe and M. Kloft, Tetrahedron Lett., 2145 (1977)
- Hennicke , H. 1906 . Justus Liebigs Ann. Chem. , 344 : 24 E. Bergmann, J. Chem. Soc. 1361 (1935)
- That the inability of cinnamyl thiocyanate to undergo the (3,3) isomerization is a thermodynamic problem has been demonstrated by Iliceto and Gaggia2f who isolated only cinnamyl thiocyanate in attempting to prepare α-phenylallyl isothiocyanate from α-phenylallyl amine and carbon disulfide
- de la Mare , P. B. D. 1952 . J. Chem. Soc. , : 1602
- Vellux , L. 1953 . Substances naturelles de synthèse , 7 : 31
- Hoppe , D. and Kloft , M. 1976 . Justus Liebigs Ann. Chem. , : 1850
- Yields reported have not been optimized and refer to isolated products with satisfactory elemental analysis and/or exact mass molecular weights
- Isothiocyanate 2a appears to be one isomer and presumably has the z configuration; 2c and 2d appear as a mixture of isomers
- This procedure does not appear to have general utility with acyclic α,ß-unsaturated ketones or nitriles
- Englehart , J. E. and McDivitt , J. R. 1971 . J. Org. Chem. , 36 : 367
- Stork , G. and Kreft , A. F. III . 1977 . J. Am. Chem. Soc. , 99 : 3850 For an excellent review of the SN2 reaction, see G. Stork and A. F. Kreft III, J. Am. Chem. Soc., 99, 3851 (1977)
- Cook , A. H. , Elvidge , J. A. and Shaw , G. 1949 . J. Chem. Soc. , : 2367
- Baldwin , J. E. , Cutting , J. , Dupont , W. , Kruse , L. , Silberman , L. and Thomas , R. C. 1976 . J. Chem. Soc., Chem. Commun. , : 736 The mechanism for the formation of 13 has not been defined but could be viewed as a 6 π electrocyclic process or possibly a 5-endo-trig ring closure since the geometric constraints for such a closure do not appear critical with a sulphur nucleophile. See