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Mechanism and Diastereoselectivity of [3+3] Cycloaddition between Enol Diazoacetate and Azomethine Imine Catalyzed by Dirhodium Tetracarboxylate: A Theoretical Study
Author(s) -
Zhang Yan,
Yang Yongsheng,
Zhao Jianming,
Xue Ying
Publication year - 2018
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201800261
Subject(s) - chemistry , cycloaddition , imine , carbene , intramolecular force , medicinal chemistry , furan , rhodium , steric effects , ethyl diazoacetate , enol , stereochemistry , catalysis , organic chemistry , cyclopropanation
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.