ABSTRACT
This study is focused on describing the molecular mechanism beyond the molecular picture provided by the evolution of molecular orbitals, valence bond structures along the reaction progress, or conceptual density functional theory. Using bonding evolution theory (BET) analysis, we have deciphered the mechanism of the 1,3-dipolar rearrangement between acetonitrile oxide and (1S,2R,4S)-2-cyano-7-oxabicyclo[2.2.1]hept-5-en-2-yl acetate derivatives. The BET study revealed that the formation of the C-C bond takes place via a usual sharing model before the O-C one that is also formed in the halogenated species through a not very usual sharing model. The mechanism includes depopulation of the electron density at the N-C triple bond and creation of the V(N) and V(C) monosynaptic basins, depopulation of the former C-C double bond with the creation of V(C,C) basins, and final formation of the V(O,C) basin associated with the O-C bond. The topological changes along the reaction pathway take place in a highly synchronous way. BET provides a convenient quantitative method for deriving curly arrows and electron flow representation to unravel molecular mechanisms.