Influence of Lewis acids on the Diels–Alder reaction. Part I. An improved synthesis of 7-azanorbornadiene, 3-azaquadricyclane, and azepine derivatives

Bansal, R. C.; Mcculloch, A. W.; McInnes, A. G.

doi:10.1139/v69-390

Cited by 49 publications

(12 citation statements)

References 7 publications

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“…Consequently 5 is isolated in the AlC1,-promoted reaction as the predominant diadduct since this kinetically-controlled product forms a reasonably stable complex with the Lewis acid, thus inhibiting retrogression and subsequent equilibration. This behavior is similar to that which we have observed previously with monoadducts of pyrroles and other furans with DMAD which also form complexes with AlCl, (1,2).…”

Section: Aic1-promoted Reactionsupporting

confidence: 90%

Influence of Lewis Acids on the Diels–Alder Reaction. V. The Reaction of Furan with Dimethyl Acetylenedicarboxylate

Mcculloch¹,

Smith²,

McInnes³

1973

Can. J. Chem.

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The Diels-Alder addition of furan to dimethyl acetylenedicarboxylate (DMAD) affords a monoadduct 1. The position and steric course of further addition of furan to the latter are temperature dependent. At temperatures of 50" or below addition occurs mainly at the activated double bond to give et~do-endo 4 and endo-exo 5 diadducts. At 100" addition occurs at the less substituted double bond of the monoadduct to give analogous etrdo-endo 7 and endo-exo 9 diadducts; further addition of furan to the latter at 100' affords four triadducts 12-15. The configurations of all these products were determined by p.m.r. and assignments confirmed by simulation of the spectra.AICI, causes enormous rate enhancement of the Diels-Alder additions of furan to DMAD and to the activated double bond of the monoadduct. In the presence of the Lewis acid the predominant diadduct formed is the endo-exo isomer 5.L'addition du type Diels-Alder du furanne sur I'acCtylenedicarboxylate de dimithyle (DMAD) conduit au produit de monoaddition 1. La positio~l et le mecanisme sterique d'additions supplCmentaires du furanne sur le produit 1 dependent de la temperature. A 50 "C ou en-dessous I'addition se produit principalement sur la double liaison activee pour donner des produits de double addition endo-endo 4 et endo-exo 5. A 100 "C, I'addition se produit sur la double liaison la moins substituie du produit de monoaddition pour donner les produits de double addition analogues et~do-endo 7 et endo-exo 9; des additions supplCmentaires du furanne sur ces derniers produits a 100 "C conduisent a quatre produits de triple addition 12-15. Les configurations de tous ces produits ont CtC dCterminCes par r.m.n. e t les attributions ont CtC confirmkes par simulation des spectres.Le AICI, entraine une augmentation enorme de la vitesse d'addition du type Diels-Alder du furanne sur le DMAD et sur la double liaison activke du oroduit de monoaddition. En oresence de I'acide deLewis. Ie produit majeur de double addition form6 est l'isomkre etldo-e.ro 5.

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Section: Aic1-promoted Reactionsupporting

confidence: 90%

Influence of Lewis Acids on the Diels–Alder Reaction. V. The Reaction of Furan with Dimethyl Acetylenedicarboxylate

Mcculloch¹,

Smith²,

McInnes³

1973

Can. J. Chem.

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“…34,38 Variation of the reaction temperature and the ratio of aluminum trichloride to addends were found to lead to low yields of the desired cycloaddition adducts where the corresponding 2-substituted pyrroles 8 and 9 were obtained as the major products.…”

Section: A Lewis Acid Catalyzed Reactionsmentioning

confidence: 99%

Chemistry of 7-Azabicyclo[2.2.1]hepta-2,5-dienes, 7-Azabicyclo[2.2.1]hept-2-enes, and 7-Azabicyclo[2.2.1]heptanes

1996

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ContentsI. Introduction 1179 II. Preparation of 7-Azabicyclo[2.2.1]hepta-2,5-dienes and 7-Azabicyclo[2.2.1]hept-2-enes by the [4+2] Cycloaddition Reaction 1179 A. Lewis Acid Catalyzed Reactions 1181 B. High-Pressure and Ultrasound Reactions 1182 C. Reactions with Acetylene Equivalents 1183 D. Miscellaneous Reactions 1183 III. Chemistry of the 7-Azabicyclo[2.2.1]hepta-2,5-dienes and 7-Azabicyclo[2.2.1]hept-2-enes 1184 A. Synthesis of Substituted Pyrroles 1184 B. Synthesis of Substituted Arene Derivatives 1185 C. Synthesis of the Organometallic Complexes 1187 IV. Synthetic Approaches to the 7-Azabicyclo[2.2.1]heptanes 1187 A. Intramolecular Cyclization of Cyclohexylamine Derivatives 1187 B. Reduction of 7-Azabicyclo[2.2.1]hepta-2,5-dienes and 7-Azabicyclo[2.2.1]hept-2-enes 1188 C. [3+2] Cycloaddition Reactions 1189 D. Intramolecular Cyclization of Substituted Proline Derivatives 1189 E. Miscellaneous Reactions 1190 V. Properties of 7-Azabicyclo[2.2.1]heptane Derivatives 1190 A. 7-Azabicyclo[2.2.1]heptane and 7-Azabicyclo-[2.2.1]heptene Derivatives as Potential Chemotherapeutic Drugs 1190

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“…Although the DielsAlder synthesis of the 7-azabicyclo [2.2.1 Iheptane skeleton via the reaction of N-substituted pyrroles with acetylenic dienophiles had been reported (9), the low yields (< 9 %) in all reactions made this route seem unattractive. Recently, Shafi'ee and Hite described improved yields for the Diels-Alder reaction in the synthesis of the N-carbobenzoxy derivative of 7-azabicyclo [2.2.1]-hept-2-ene-2-carboxylic acid (12) and in the past year the use of aluminum chloride as a catalyst was shown to improve the yield of the product from reaction of N-carbomethoxypyrrole with acetylene dicarboxylic ester to 93 % (6).…”

Section: Synt/zesis Ofmentioning

confidence: 99%

Synthesis of 7-azabicyclo[2.2.1]heptane, exo-2-chloro-7-azabicyclo[2.2.1]heptane, and derivatives

Fraser¹,

Swingle²

1970

Can. J. Chem.

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A synthesis of 7-azabicyclo[2.2.1]heptane (1) in five steps and an overall yield of 18 % has beenachieved. An alternative five-step route which gives 1 in 36% yield but which requires large amounts of platinum oxide has also been developed. In comparison, the only previous synthesis of this con~pound gave less than a 1 % overall yield of an impure product. Several N-acyl derivatives and the N-n~troso derivative have been prepared, and the barriers to rotation about the N-CO bond of the acetyl derivative and the N-NO bond of the nitroso derivative have been determined. The barriers were found to be 1.2 and 6.5 kcal less, respectively, than in their unstrained analogs. exo-2-Chloro-7-azabicyclo[2.2.l]heptane has also been synthesized.Canadian Journal of Chemistry, 48,2065Chemistry, 48, (1970 Considerable interest has recently developed in the nitrogen analogs of bicyclo [2.2.1 Iheptane. Reports on the synthesis and reactions of compounds containing nitrogen in the 1-position (1,2) and in the 2-position (3,4) have appeared. The 7-azabicyclo[2.2.1]heptane system has perhaps received more attention. In particular, many highly substituted derivatives have been produced by the Diels-Alder reactions of N-alkyl and N-acyl pyrroles with dimethylacetylene dicarboxylate (5-12). In contrast the parent 7-azabicyclo [2.2.1 Iheptane (1) was reported as synthesized only in impure form and was characterized by conversion to a picrate and a 7,7-dimethiodide derivative (12). Its synthesis from hydroquinone involved seven steps and gave 1 in an overall yield of less than 1 %. We wish to report an improvement in the synthesis of 1, which allows its preparation in yields of up to 36 %. The proof of structure of 1 is supported by its conversion to five derivatives, two of which are the subject of a temperature-dependent nuclear magnetic resonance (n.m.r.) investigation. In addition the exo-2-chloro derivative of 1 was synthesized and preliminary studies of its reactivity are reported.

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Influence of Lewis acids on the Diels–Alder reaction. Part I. An improved synthesis of 7-azanorbornadiene, 3-azaquadricyclane, and azepine derivatives

Cited by 49 publications

References 7 publications

Influence of Lewis Acids on the Diels–Alder Reaction. V. The Reaction of Furan with Dimethyl Acetylenedicarboxylate

Influence of Lewis Acids on the Diels–Alder Reaction. V. The Reaction of Furan with Dimethyl Acetylenedicarboxylate

Chemistry of 7-Azabicyclo[2.2.1]hepta-2,5-dienes, 7-Azabicyclo[2.2.1]hept-2-enes, and 7-Azabicyclo[2.2.1]heptanes

Synthesis of 7-azabicyclo[2.2.1]heptane, exo-2-chloro-7-azabicyclo[2.2.1]heptane, and derivatives

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