А Quantum‐Chemical Study of the Mechanism of 1‐Azadienes Formation from Aldimines and Arylacetylenes in the KOtBu/DMSO Superbasic Medium DOI
Vladimir B. Orel, A. A. Zubarev, N. M. Vitkovskaya

et al.

Asian Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 14, 2024

Abstract The mechanism of 1‐azadienes formation from aldimines and arylacetylenes in the KO t Bu/DMSO superbasic medium has been explored theoretically using a DFT approach [B2PLYP(D2)/6‐311+G(d,p)//B3LYP/6‐31+G(d)] sophisticated model taking potassium tert ‐butoxide nearest solvation shell cation explicitly into account. main focus is placed on (i) detailed analysis kinetic thermodynamic characteristics isomerization intermediate propargylamine 1‐azadienes, (ii) factors determining isomeric composition with different substituents starting arylaldimines arylacetylenes. Our findings clearly indicate that mild experimental conditions are accounted for by relatively small activation barrier (Δ G ≠ ≤16.2 kcal/mol) limiting step (ethynylation aldimine arylacetylenes). rapid to 1‐azadiene found be due low barriers ≤9.1 related protons transfer. case various substituted determined solely difference stability 1 E ,2 ‐ Z ‐forms.

Language: Английский

А Quantum‐Chemical Study of the Mechanism of 1‐Azadienes Formation from Aldimines and Arylacetylenes in the KOtBu/DMSO Superbasic Medium DOI
Vladimir B. Orel, A. A. Zubarev, N. M. Vitkovskaya

et al.

Asian Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 14, 2024

Abstract The mechanism of 1‐azadienes formation from aldimines and arylacetylenes in the KO t Bu/DMSO superbasic medium has been explored theoretically using a DFT approach [B2PLYP(D2)/6‐311+G(d,p)//B3LYP/6‐31+G(d)] sophisticated model taking potassium tert ‐butoxide nearest solvation shell cation explicitly into account. main focus is placed on (i) detailed analysis kinetic thermodynamic characteristics isomerization intermediate propargylamine 1‐azadienes, (ii) factors determining isomeric composition with different substituents starting arylaldimines arylacetylenes. Our findings clearly indicate that mild experimental conditions are accounted for by relatively small activation barrier (Δ G ≠ ≤16.2 kcal/mol) limiting step (ethynylation aldimine arylacetylenes). rapid to 1‐azadiene found be due low barriers ≤9.1 related protons transfer. case various substituted determined solely difference stability 1 E ,2 ‐ Z ‐forms.

Language: Английский

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