Diels−Alder Reaction of Heterocyclic Imine Dienophiles

Hedberg, Christian; Pinho, Pedro; Roth, Peter; Andersson, Pher G.

doi:10.1021/jo9916683

Cited by 39 publications

(34 citation statements)

References 19 publications

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“…6 On the other hand, the I-DA reaction of diprotonated iminium cation 4, u ¼ 22.79 eV, with Cp 2 (ref. 10) presented a twostep mechanism with formation of cationic intermediate IN (see Scheme 3). 7 Similar to the I-DA reactions of 1 with Cp 2, TS1 was found to be À17 kcal mol À1 below the reagents.…”

Section: Introductionmentioning

confidence: 99%

The mechanism of ionic Diels–Alder reactions. A DFT study of the oxa-Povarov reaction

2014

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Section: Introductionmentioning

confidence: 99%

The mechanism of ionic Diels–Alder reactions. A DFT study of the oxa-Povarov reaction

2014

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“…The Diels-Alder reaction is one of the most useful methods to make six-member heterocycles, and has attracted considerable interest both experimentally [1][2][3][4][5][6][7][8] and theoretically [9][10][11][12][13][14]. Semi-empirical calculations of intraand inter-molecular Diels-Alder systems have been shown to be in good agreement with experiment for cycloaddition reactions [15][16][17].…”

Section: Introductionmentioning

confidence: 99%

Theoretical Study of the Mechanism of an Inverse-Demand Diels–Alder Reaction

Shihab

2011

Arab J Sci Eng

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Quantum mechanical calculations (AM1, PM3, ab initio HF/3-21G, DFT(B3LYP/6-31G*) and MP2 //(B3LYP/6-31G*) have been used to study the inverse-demand synchronous concerted Diels-Alder reactions between dimethyl-1,2,4,5-tetrazine-3,6-dicarboxylate (diene) and a variety of dienophiles (ethylene, cyclopentadiene, 1-hexene, cyclohexene). All the molecular structures (reactants, transition states, intermediates and adducts) were optimized using the semi-empirical AM1 method. The calculated energies and volumes showed that the cycloaddition reaction followed a mechanism involving the formation of an intermediate, elimination of N 2 , and a 1,3-hydrogen shift adduct. The reaction energies of the systems were obtained by using semi-empirical AM1 calculations and showed good agreement with the experimental data. In contrast, calcula

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“…Andersson and co-workers investigated the synthesis of epibatidine, an alkaloid found on the skin of the endangered Equadorian frog. [70] Since its isolation, a large amount of attention has been devoted to the development of a direct synthesis or the preparation of analogues that might have higher analgesic activity and lower toxicity. Anderssons group have exploited the good versatility of the iADA reaction to prepare a wide range of analogues of epibatidine that contain the two nitrogen atoms close to each other.…”

Section: Entry Diene T [H]mentioning

confidence: 99%

“…Andersson and co‐workers investigated the synthesis of epibatidine, an alkaloid found on the skin of the endangered Equadorian frog 70. Since its isolation, a large amount of attention has been devoted to the development of a direct synthesis or the preparation of analogues that might have higher analgesic activity and lower toxicity.…”

Section: Asymmetric Iada Cycloadditionsmentioning

confidence: 99%

Iminium Ions as Dienophiles in Aza‐Diels–Alder Reactions: A Closer Look

Memeo

Quadrelli

2012

Chemistry A European J

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This review highlights the state of the art of the use of iminium ions as dienophiles in Aza-Diels-Alder (ADA) cycloadditions. An historical survey spanning the very first discovery of the reaction to modern developments, mechanistic studies and synthetic applications of the iminium variant of the ADA (iADA) reaction are presented. The discussion is focused on the intermolecular and intramolecular versions of the iADA reactions that are conducted in aqueous solutions to generate, in situ, the reactive dienophile from an amine hydrochloride and either aliphatic or aromatic aldehydes in the presence of a variety of dienes. The retro-ADA reaction is also presented as an interesting method for the protection of amines. The use of Lewis acid catalysis in these reactions was thoroughly studied by the reactions of different amines and aldehydes conducted in the presence of lanthanide(III) complexes.

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Diels−Alder Reaction of Heterocyclic Imine Dienophiles

Cited by 39 publications

References 19 publications

The mechanism of ionic Diels–Alder reactions. A DFT study of the oxa-Povarov reaction

The mechanism of ionic Diels–Alder reactions. A DFT study of the oxa-Povarov reaction

Theoretical Study of the Mechanism of an Inverse-Demand Diels–Alder Reaction

Iminium Ions as Dienophiles in Aza‐Diels–Alder Reactions: A Closer Look

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