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Mechanistic Insight Into the AuCN Catalyzed Annulation Reaction of Salicylaldehyde and Aryl Acetylene: Cyanide Ion Promoted Umpolung Hydroacylation/Intramolecular Oxa-Michael Addition Mechanism
- Source :
- Frontiers in Chemistry, Vol 7 (2019), Frontiers in Chemistry
- Publication Year :
- 2019
- Publisher :
- Frontiers Media SA, 2019.
-
Abstract
- The detailed mechanism of the AuCN-catalyzed annulation of salicylaldehyde (SA) and phenyl acetylene leading to isoflavanone-type complexes has been investigated via density functional theory (DFT) calculations. Reaction pathways and possible stationary points are obtained with the combined molecular dynamics and coordinate driving (MD/CD) method. Our calculations reveal that the cyanide ion promoted umpolung hydroacylation/intramolecular oxa-Michael addition mechanism is more favorable than the Au(I)/Au(III) redox mechanism proposed previously. In the umpolung mechanism, the hydroxyl of SA is found to strongly stabilize the cyanide ion involved intermediates and transition states via hydrogen bond interaction, while the Au(I) ion always acts as a counter cation. The overall reaction is exergonic by 41.8 kcal/mol. The hydroacylation of phenyl acetylene is the rate-determining step and responsible for the regioselectivity with a free energy barrier of 27.3 kcal/mol. These calculated results are in qualitative accord with the experimental findings.
- Subjects :
- Annulation
Hydroacylation
02 engineering and technology
010402 general chemistry
DFT
01 natural sciences
Medicinal chemistry
Umpolung
lcsh:Chemistry
chemistry.chemical_compound
cyanide ion
Original Research
Exergonic reaction
hydroacylation
General Chemistry
021001 nanoscience & nanotechnology
umpolung
Transition state
0104 chemical sciences
Chemistry
lcsh:QD1-999
Salicylaldehyde
chemistry
Phenylacetylene
Intramolecular force
MD/CD
0210 nano-technology
Subjects
Details
- ISSN :
- 22962646
- Volume :
- 7
- Database :
- OpenAIRE
- Journal :
- Frontiers in Chemistry
- Accession number :
- edsair.doi.dedup.....7fb90d9b236a201bb9d0dc79aee0a195