Abstract
The theoretical study reported in the present work deals with chiral cyclic vinyl sulfilimines and their reactivity as dienophiles in [4 + 2] cycloaddition reactions, using B3LYP/6-31G(d)//AM1 and B3LYP/6-31G(d)//B3LYP/6-31G(d) model chemistries. Consideration of Lewis acid catalysis, illustrated by BF3, decreases the activation energies of the cycloaddition process while the charge transfer from the diene to the sulfilimine is augmented. The [4 + 2] cycloaddition reactions of sulfilimines with both furan and cyclopentadiene occur in the gas phase with endo stereoselectivity, which is more pronounced with the latter diene. Endo-exo energy differences in the gas phase with the B3LYP/6-31+G(d)//B3LYP/6-31+G(d), B3LYP/6-31G(d)//B3LYP/6-31G(d), and B3LYP/6-31G-(d)//AM1 model chemistries are almost the same. Solvent effects are responsible for the inversion of the stereoselectivity in the reactions of sulfilimines with furan because of the great difference in the dipole moments in endo and exo approaches.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 2926-2933 |
| Number of pages | 8 |
| Journal | Journal of Organic Chemistry |
| Volume | 67 |
| Issue number | 9 |
| DOIs | |
| State | Published - May 3 2002 |
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ASJC Scopus subject areas
- Organic Chemistry
Cite this
Cyclic vinyl p-tolyl sulfilimines as chiral dienophiles : Theoretical study on the stereoselectivity, Lewis acid catalysis, and solvent effects in their Diels-Alder reactions. / García Ruano, José L.; Clemente, Fernando R.; González Gutiérrez, Lorena; Gordillo, Ruth; Martín Castro, Ana M.; Rodríguez Ramos, Jesús H.
In: Journal of Organic Chemistry, Vol. 67, No. 9, 03.05.2002, p. 2926-2933.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Cyclic vinyl p-tolyl sulfilimines as chiral dienophiles
T2 - Theoretical study on the stereoselectivity, Lewis acid catalysis, and solvent effects in their Diels-Alder reactions
AU - García Ruano, José L.
AU - Clemente, Fernando R.
AU - González Gutiérrez, Lorena
AU - Gordillo, Ruth
AU - Martín Castro, Ana M.
AU - Rodríguez Ramos, Jesús H.
PY - 2002/5/3
Y1 - 2002/5/3
N2 - The theoretical study reported in the present work deals with chiral cyclic vinyl sulfilimines and their reactivity as dienophiles in [4 + 2] cycloaddition reactions, using B3LYP/6-31G(d)//AM1 and B3LYP/6-31G(d)//B3LYP/6-31G(d) model chemistries. Consideration of Lewis acid catalysis, illustrated by BF3, decreases the activation energies of the cycloaddition process while the charge transfer from the diene to the sulfilimine is augmented. The [4 + 2] cycloaddition reactions of sulfilimines with both furan and cyclopentadiene occur in the gas phase with endo stereoselectivity, which is more pronounced with the latter diene. Endo-exo energy differences in the gas phase with the B3LYP/6-31+G(d)//B3LYP/6-31+G(d), B3LYP/6-31G(d)//B3LYP/6-31G(d), and B3LYP/6-31G-(d)//AM1 model chemistries are almost the same. Solvent effects are responsible for the inversion of the stereoselectivity in the reactions of sulfilimines with furan because of the great difference in the dipole moments in endo and exo approaches.
AB - The theoretical study reported in the present work deals with chiral cyclic vinyl sulfilimines and their reactivity as dienophiles in [4 + 2] cycloaddition reactions, using B3LYP/6-31G(d)//AM1 and B3LYP/6-31G(d)//B3LYP/6-31G(d) model chemistries. Consideration of Lewis acid catalysis, illustrated by BF3, decreases the activation energies of the cycloaddition process while the charge transfer from the diene to the sulfilimine is augmented. The [4 + 2] cycloaddition reactions of sulfilimines with both furan and cyclopentadiene occur in the gas phase with endo stereoselectivity, which is more pronounced with the latter diene. Endo-exo energy differences in the gas phase with the B3LYP/6-31+G(d)//B3LYP/6-31+G(d), B3LYP/6-31G(d)//B3LYP/6-31G(d), and B3LYP/6-31G-(d)//AM1 model chemistries are almost the same. Solvent effects are responsible for the inversion of the stereoselectivity in the reactions of sulfilimines with furan because of the great difference in the dipole moments in endo and exo approaches.
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U2 - 10.1021/jo016175o
DO - 10.1021/jo016175o
M3 - Article
VL - 67
SP - 2926
EP - 2933
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
SN - 0022-3263
IS - 9
ER -