Theoretical investigation of the stereoselectivity of some Diels–Alder reactions involving cyclopentadiene

Zhao, Dong Xia; Xu, Zhen; Yang, Zhong Zhi

doi:10.1016/j.cclet.2008.06.023

Cited by 3 publications

(1 citation statement)

References 18 publications

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“…[ 24,26‐33 ] Especially, D‐A reactions in pericyclic reactions were gained widespread investigations by the conceptual density functional theory (CDFT). [ 26,29‐30,34‐36 ] Domingo et al . [ 28 ] have shown that the classification of diene and dienophile pairs with a unique scale of electrophilicity is a useful tool for predicting the reaction mechanism and regioselectivity of D‐A reactions.…”

Section: Background and Originality Contentmentioning

confidence: 99%

Theoretical Investigation on Regioselectivities of Diels‐Alder Reactions by Conjugated Effect

Zhao

et al. 2020

Chin. J. Chem.

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of main observation and conclusion The regioselectivities of 76 Diels-Alder reactions between unsymmetrical dienes and dienophiles were investigated by local softness and generalized local softness at atomic and chemical bond view, respectively, where the reactivity descriptors were calculated by finite difference approximation and ABEEMσπ model. Based on local HSAB principle and matching criterion of local softness, reasonable explanation and prediction on regioselectivities of all reactions through ABEEMσπ model have been obtained, which are in agreement with the experimental results. Especially, at π-bond level, while the 1-substituents of dienes were NH2, NMe2, and NEt2, because of the p-π conjugated effect between the lone pairs of N atom and the conjugated π-bond of the four double-bonded carbon atoms in diene, it made the dienophile not easy to approach diene by Manner A, hence, Manner B can forecast the ortho regioisomer as main product well, and Manner A cannot. As to the other reactions, both Manner A and Manner B can predict their regioselectivities. It can be seen that the ABEEMσπ model can take the effect of the chemical environment on the reaction reactivity into account richly, especially the system includes π-bond and lone pairs. However, the results through the finite difference approximation are not reasonable. Background and Originality Content Diels-Alder (D-A) reaction is one of the most useful synthetic reactions, and its overwhelming importance is well known in organic synthesis of six-membered functionalized carbocyclic compounds. The usefulness of D-A reaction arises from its versatility and from its remarkable regio-and stereoselectivity. The reaction between unsymmetrical diene and dienophile can produce two isomeric adducts depending on the orientation of the substituents in the dienes, as shown in Figure 1.

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Section: Background and Originality Contentmentioning

confidence: 99%

Theoretical Investigation on Regioselectivities of Diels‐Alder Reactions by Conjugated Effect

Zhao

et al. 2020

Chin. J. Chem.

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Density functional theory study of the regio‐ and stereoselectivity of diels–alder reactions of 5‐Aryl‐2‐pyrones

Chemouri

Mekelleche

2011

Int J of Quantum Chemistry

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A theoretical study of the mechanism and regio-and stereoselectivity of Diels-Alder reactions of 5-aryl-2-pyrones (Ar ¼ Ph, 4-(MeS)-Ph) with substituted alkenes (CHZ ¼ CH 2 , Z ¼ COMe, OAc) is performed at the B3LYP/6-31G(d) level. The analysis of the relevant stationary points of the potential energy surface and intrinsic reaction coordinate calculations show that these cycloadditions are undergoing through asynchronous concerted mechanisms yielding to the formation of the 5-endo isomers as the major cycloadducts. The calculation of activation and reaction energies indicates that the 5-endo cycloadducts are favored both kinetically and thermodynamically. The obtained results are in good agreement with experimental outcomes.

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Chiral supramolecular catalysts of helical nanoribbon: more twist, higher enantioselectivity

Gao,

Zhu,

et al. 2024

Chinese Chemical Letters

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Theoretical investigation of the stereoselectivity of some Diels–Alder reactions involving cyclopentadiene

Cited by 3 publications

References 18 publications

Theoretical Investigation on Regioselectivities of Diels‐Alder Reactions by Conjugated Effect

Theoretical Investigation on Regioselectivities of Diels‐Alder Reactions by Conjugated Effect

Density functional theory study of the regio‐ and stereoselectivity of diels–alder reactions of 5‐Aryl‐2‐pyrones

Chiral supramolecular catalysts of helical nanoribbon: more twist, higher enantioselectivity

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