TY - JOUR
T1 - Distortion Rules
T2 - Diene Ring Size Effects in Diels-Alder Reactions with Triazolinediones
AU - Hernández-Mancera, Jennifer Paola
AU - Rojas-Valencia, Natalia
AU - Núñez-Zarur, Francisco
N1 - Publisher Copyright:
© 2024 Wiley-VCH GmbH.
PY - 2024/1/8
Y1 - 2024/1/8
N2 - Triazolinediones (TADs) are highly reactive electrophiles used in several processes within the field of organic chemistry, especially in Diels-Alder cycloadditions. The reactions of TADs with cyclic dienes have been observed to depend on the diene structure and size. To investigate the role of diene structure in the reactivity of TADs, computational chemistry based on DFT and Activation Strain Model were employed to quantitatively assess the impact of distortion and interaction energies on the observed reactivity. Calculations suggest that the reactions are endo selective based on lower energy barriers compared to the exo pathway. Additionally, the trends in reactivity agree with experimental observations: cyclopentadiene is the more reactive diene, followed by cyclohexadiene and cycloheptadiene. The ASM analysis reveals that this trend is a consequence of the degree of distortion the reactants along the reaction coordinate. These distortion energies also allowed to explain why the endo selective route is preferred over the exo one.
AB - Triazolinediones (TADs) are highly reactive electrophiles used in several processes within the field of organic chemistry, especially in Diels-Alder cycloadditions. The reactions of TADs with cyclic dienes have been observed to depend on the diene structure and size. To investigate the role of diene structure in the reactivity of TADs, computational chemistry based on DFT and Activation Strain Model were employed to quantitatively assess the impact of distortion and interaction energies on the observed reactivity. Calculations suggest that the reactions are endo selective based on lower energy barriers compared to the exo pathway. Additionally, the trends in reactivity agree with experimental observations: cyclopentadiene is the more reactive diene, followed by cyclohexadiene and cycloheptadiene. The ASM analysis reveals that this trend is a consequence of the degree of distortion the reactants along the reaction coordinate. These distortion energies also allowed to explain why the endo selective route is preferred over the exo one.
KW - activation strain model
KW - computational chemistry
KW - cyclic diene
KW - density functional calculations
KW - Diels-Alder
KW - triazolinedione
UR - http://www.scopus.com/inward/record.url?scp=85181458312&partnerID=8YFLogxK
U2 - 10.1002/slct.202304683
DO - 10.1002/slct.202304683
M3 - Artículo
AN - SCOPUS:85181458312
SN - 2365-6549
VL - 9
JO - ChemistrySelect
JF - ChemistrySelect
IS - 1
M1 - e202304683
ER -