Abstract
The mechanism and diastereoselectivity of the dirhodium‐catalyzed [3+3] cycloaddition reaction between an enol diazoacetate and an azomethine imine in toluene to produce bicyclic pyrazolidinone derivatives have been investigated by DFT at the M06‐GD3/6‐311+G(2d,2p) [Rh‐RSC+4f]//M06‐GD3/6‐31G(d,p) [Rh‐RSC+4f] level combined with the solvation SMD model. The results revealed that the reaction process, beginning with the rhodium–carbene active intermediate, occurs in two steps: Vinylogous addition (C–N bond forming) and intramolecular six‐numbered ring closure (C–C bond forming), with the second step being rate‐limiting. Furthermore, the origin of the diastereoselectivity was investigated by orbital composition analysis, distortion/interaction analysis, and natural bond orbital calculations and found to be a result of steric and electronic effects.
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