One-pot synthesis of chromenylfurandicarboxylates and cyclopenta[b]chromenedicarboxylates involving zwitterionic intermediates. A DFT investigation on the regioselectivity of the reaction.
The reaction of 1:1 zwitterionic intermediates generated in situ from either tert-butylisocyanide or cyclohexylisocyanide and acetylenedicarboxylates with 3-formylchromones is described, whereupon either chromenylfurandicarboxylates or cyclopenta[b]chromenedicarboxylates are formed, depending on the nature of the chromone 6-position substituent and also on the acetylene ester group. In addition, from the reaction with a 1:2 zwitterionic intermediate, cyclohepta[b]chromenetetracarboxylates are isolated. The regioselectivity of the reaction was also investigated by DFT calculations. The geometries of the reactants, intermediate zwitterions, transition structures, and intermediate products, leading to the final products, were optimized using the B3LYP functional with the 6-31G(d) basis set. The structures of the products were elucidated by 1D and 2D NMR experiments. Full assignment of all (1)H and (13)C NMR chemical shifts has been achieved. Plausible mechanistic schemes are provided.
Terzidis
Michael A
MA
Department of Chemistry, Laboratory of Organic Chemistry, University of Thessaloniki, Thessaloniki 54124, Macedonia, Greece.
Stephanidou-Stephanatou
Julia
J
Tsoleridis
Constantinos A
CA
D001578:Benzopyrans / Q000737:chemistry*; D002264:Carboxylic Acids / Q000737:chemistry*; D003517:Cyclopentanes / Q000737:chemistry*; D005663:Furans / Q000737:chemistry*; D015394:Molecular Structure; D011789:Quantum Theory; D013237:Stereoisomerism
D001578:Benzopyrans; D002264:Carboxylic Acids; D003517:Cyclopentanes; D005663:Furans