Abstract
Recent applications of theoretical and physical approaches to the elucidation of acyl-transfer mechanisms have led to further clarifications of structures of intermediates and transition states involved in the stepwise reaction paths. Gas-phase acyl-transfer reactions, both experimental and theoretical, are surveyed, in which factors conductive to the stepwise path are discussed. Aminolysis reactions of carbonyl and thiocarbonyl esters in solution are reviewed with special emphasis of transition state variation with substituents in the nucleophile, acyl and leaving groups applying Marcus theory, Bell-Evans-Palanyi principle, principle of microscopic reversibility, DFTFukui function, reactivity-selectivity principle, natural bond orbital analysis and More OFerrall-Jencks diagram etc. The use of cross-interaction constants as a mechanistic tool is stressed.
Keywords: acyl-transfer reactions, bond orbital analysis, cross-interaction constants, mechanistic tool
Call for Papers in Thematic Issues
Catalytic C-H bond activation as a tool for functionalization of heterocycles
The major topic is the functionalization of heterocycles through catalyzed C-H bond activation. The strategies based on C-H activation not only provide straightforward formation of C-C or C-X bonds but, more importantly, allow for the avoidance of pre-functionalization of one or two of the cross-coupling partners. The beneficial impact of ...read more
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