| Abstract: | Abstract The thermal cycloaddition between thiobenzophenones (1) and ketenimines (2) takes place according to two reaction modes, the stereochemical course being determined by the type of substituent at nitrogen on the cumulene. Specifically, N-arylketenimines (2a) (X = H) react with (1) as a formal 4π system giving as final products 4H-3,1-benzothiazines (3) (1,4-cyclisation), whereas N-aryl ortho-disubstituted compounds (2b) (X = Me), as well as N-alkyl derivatives (2c), behave as 2π component to give 2-iminothietans (4) (1,2-cyclisation) (Scheme I). In the formation of the six membered ring compound (3), the ketenimine (2a) can be viewed to act as a 1,4-heterodiene to give the intermediate (3a) by addition of (1) across the Cdbnd]N bond and the Cdbnd]C of the N-aryl ring. Both reactions proved to be stereoselective. |
