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Concerted vs. Non‐Concerted 1,3‐Dipolar Cycloadditions of Azomethine Ylides to Electron‐Deficient Dialkyl 2,3‐Dicyanobut‐2‐enedioates
Author(s) -
Khlebnikov Alexander F.,
Konev Alexander S.,
Virtsev Alexander A.,
Yufit Dmitry S.,
Mlostoń Grzegorz,
Heimgartner Heinz
Publication year - 2014
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.201300405
Subject(s) - cycloaddition , azomethine ylide , chemistry , zwitterion , ylide , dimethyl acetylenedicarboxylate , concerted reaction , steric effects , electrocyclic reaction , 1,3 dipolar cycloaddition , photochemistry , medicinal chemistry , computational chemistry , stereochemistry , molecule , bicyclic molecule , organic chemistry , catalysis
The quantum‐chemical calculations of the thermal ring opening of 1‐methyl‐2,3‐diphenyl‐ and 1,2,3‐triphenylaziridine with formation of the corresponding azomethine ylides of S‐, U‐, and W‐type as well as their cycloaddition to dimethyl acetylenedicarboxylate (DMAD) and dimethyl 2,3‐dicyanobut‐2‐enedioate, were performed at the DFT B3LYP/6‐31G(d) level of theory with the PCM solvation model. The calculations are in complete accordance with experimental results and explain the switch from the concerted to the non‐concerted pathway depending on substituents in the dipolarophile and the ylide. It was found that strong electron‐withdrawing substituents in dipolarophiles, such as in dialkyl dicyanobutenedioates, significantly reduce the barrier for the formation of zwitterionic intermediates in the reaction of azomethine ylides with such dipoles. This can render the stepwise cycloaddition competitive with the concerted one. However, the concertedness of the cycloaddition even to dipolarophiles with several electron‐withdrawing substituents is governed by a fine balance of electronic and steric effects in both ylide and dipolarophile counterparts. The hypothesis that introduction of substituents in the azomethine ylide that destabilize the positive charge in a corresponding zwitterion will favor the concerted cycloaddition even with dialkyl dicyanobutenedioates was tested theoretically and experimentally.