Chemistry of the 1,4-Diamino-1,3-butadines. IV. The Diels-Alder Reaction<sup>1</sup>

Fegley, Marian F.; Bortnick, Newman M.; McKeever, C. H.

doi:10.1021/ja01574a040

Cited by 9 publications

(3 citation statements)

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“…Prepared from the ArBr according to method A (using catalyst P26 , 193 mg, 91%) and according to method B using cyanation kit J (190 mg, 90%). Obtained as white needles: mp 139–142 °C (lit . mp 139–141 °C); 1 H NMR (400 MHz, CDCl 3 ) 7.92–7.80 (2H, m), 7.80–7.68 (2H, m); 13 C NMR (100 MHz, CDCl 3 ) 133.6, 133.1, 116.0, 115.3; LRMS (ESI) m / z [M + H] + 129.0.…”

Section: Methodsmentioning

confidence: 99%

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Improved Substrate Scope in the Potassium Hexacyanoferrate(II)-Based Cyanation for the Synthesis of Benzonitriles and Their Heterocyclic Analogues

Richardson

Mutton

2018

J. Org. Chem.

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The use of Pd(DPEPhos)Cl (P26) as a catalyst for the formation of benzonitriles and their heterocyclic analogues provides excellent complementarity to existing catalysts, allowing highly electron-deficient heterocyclic aryl halides to be efficiently converted to the corresponding nitriles using K[Fe(CN)]) as cyanide source. This catalyst significantly enhances the scope of this reaction to include a number of substrates that are highly relevant for pharmaceutical and agrochemical applications. Importantly, not only does this cyanation method employ a nontoxic cyanide source, simple semiquantitative testing suggests that, unlike many other methods, no free cyanide is present in the reaction mixture or during a variety of potential workups, thus improving the safety aspects of this method from initial setup through to product isolation. Finally, developing and testing a series of convenient cyanation kits has allowed facile application and broader adoption of this method in our laboratories.

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Section: Methodsmentioning

confidence: 99%

“…Obtained as white needles: mp 139− 142 °C (lit. 57 1,3-Dicyanobenzene (10). 55 Prepared from the ArBr according to Method A(using catalyst P26, 188 mg, 89%) and according to Method B using cyanation kit J (152 mg, 72%).…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Improved Substrate Scope in the Potassium Hexacyanoferrate(II)-Based Cyanation for the Synthesis of Benzonitriles and Their Heterocyclic Analogues

Richardson

Mutton

2018

J. Org. Chem.

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“…Subsequently, other workers have reported that the dimethyl ester corresponding to 1 (R, = 4-methoxyphenyl; R, = H) rearranged to the analogue of 2 (R, = 4-methoxyphenyl; R, = H) in the presence of warm acetic acid (16). 4 This paper discusses in full the mechanism and experimental conditions for the conversion of 1 to 2. The derivatives 2 prepared in this way, with one exception 2a, contain three d~fferent types of substituents, one of which is a phenolic hydroxyl group.…”

Section: Introductionmentioning

confidence: 94%

Influence of Lewis acids on the Diels–Alder reaction. II. Rearrangement of 1- and 1,4-substituted diethyl 7-oxabicyclo[2•2•1]2,5-heptadiene-2,3-dicarboxylate adducts to 4- and 4,6-substituted diethyl 3-hydroxyphthalates

Mcculloch¹,

Stanovnik²,

Smith³

et al. 1969

Can. J. Chem.

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Direct formation of 4-or 4,6-alkyl and aryl substituted diethyl 3-hydroxyphthalates from the correspondingly substituted Diels-Alder adducts of 2-or 2,5-substituted fi~rans and diethyl acetylenedicarboxylate is pronloted by AICI, in CH2C12 at room temperature. The first adduct of 2,5-diphenylfuran to be isolated has been obtained from the same reaction at -20'. The aromatic compounds can be obtained alternatively by treating the adducts with BF, or H2S04: where the adducts can be prepared by conventional means this two-step procedure has resulted in greatly improved yields. Adducts of furan and furfuryl alcohol are similarly converted to substituted phenols. HCI effected conversion only in the case of adducts carrying a bridgehead aryl substituent; in all other cases HCI added to the substituted double bond. The mechanism of the adduct rearrangement is discussed.

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Diels‐Alder‐Reaktionen I: Präparative Aspekte

Sauer

1966

Angewandte Chemie

128

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Seit fast 40 Jahren beanspruchen die nach ihren Entdeckern benanntenCycloadditio;?en konjugierter Diene praparatives und mechanistisches Interesse. Die fast unerschopjliche Variierbarkeit der Komponenten dieser Einstufenreaktionen bietet Zugang zu wichtigen Verbindungsklassen. Die in dcesem Aufsafz gebotene Systematik der praparativen Anwendungen beriicksichtigt vorwiegend neuere Ergebnisse. Im spater erscheinenden zweiten Teil des Beitrags werden die mechanistischen Aspekte der Diels-Alder-Reaktionen diskutiert. A) Definition und Entdeckungsgeschichte B) Die Dienkomponente 1. Offenkettige Diene 2. Offenkettige Diene mit Heteroatomen 3. Polyene 4. 1,2-Bisrnethylencycloalkane 5. Alicyclische Diene 6. Cyclopentadienone 7. o-Chinone und o-chinoide Systeme 8. Aromaten 9. Heterocyclen 10. Olefine und nichtkonjugierte Diene C ) Die Dienophilkomponente 1. Offenkettige Alkene und Alkine 2. Allene 3. Cyclische Dienophile 4. Cyclische Azoverbindungen 5. Weitere Pienophile mit Heteroatomen I , D) Retro-Diels-Alder-Reaktionen E) Ausblick A) Definition und Entdeckungsgeschichte Die Vereinigung konjugierter Diene mit Olefinen ist nur ein spezieller Fall des allgemeineren Reaktionsschemas der Cycloadditionen [I]; auf Kosten zweier Tc-Bindungen werden bei der Bildung des sechsgliedrigen Rings (1) zwei neue o-Bindungen gekniipft. Als weitere Beispiele fur Cycloadditionen sind Epoxydationen und Carbenadditionen, Dimerisierungen von Olefinen zu Cyclobutan-Derivaten sowie 1,3-Dipolare Additionsreaktionen zu nennen I* 921. Einzelne Beispiele fur Dienadditionen nach dern Diels-Alder-Schema frnden sich bereits in der Literatur der Jahrhundertwende. Wahrend Zincke [31 die bei der Pyrolyse von 1-Hydroxy-perchlorcyclopent-3-encarbonsaure beobachtete Dimerisation des intermediar auftretenden Tetrachlor-cyclopentadienons zu Perchlotindenon (2) richtig deutete, gelang die Strukturaufklarung fiir das 1 : I-Addukt (3) aus p-Benzochinon und Cyclopentadien erst Diels und Alder [41; fruhere Strukturvorschlage von Staudinger (mit Cyclobutan-Struktur) und Albrecht enviesen sich als revisionsbediirftig. (3) H O Die Struktur der 1 : 1-Additionsverbindung (4) aus Cyclopentadien und Azodicarbonsaureester [51 deutete erstmals an, daD es sich bei diesen Additionsreaktionen der r 1

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Chemistry of the 1,4-Diamino-1,3-butadines. IV. The Diels-Alder Reaction¹

Cited by 9 publications

References 2 publications

Improved Substrate Scope in the Potassium Hexacyanoferrate(II)-Based Cyanation for the Synthesis of Benzonitriles and Their Heterocyclic Analogues

Improved Substrate Scope in the Potassium Hexacyanoferrate(II)-Based Cyanation for the Synthesis of Benzonitriles and Their Heterocyclic Analogues

Influence of Lewis acids on the Diels–Alder reaction. II. Rearrangement of 1- and 1,4-substituted diethyl 7-oxabicyclo[2•2•1]2,5-heptadiene-2,3-dicarboxylate adducts to 4- and 4,6-substituted diethyl 3-hydroxyphthalates

Diels‐Alder‐Reaktionen I: Präparative Aspekte

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Chemistry of the 1,4-Diamino-1,3-butadines. IV. The Diels-Alder Reaction1

Cited by 9 publications

References 2 publications

Improved Substrate Scope in the Potassium Hexacyanoferrate(II)-Based Cyanation for the Synthesis of Benzonitriles and Their Heterocyclic Analogues

Improved Substrate Scope in the Potassium Hexacyanoferrate(II)-Based Cyanation for the Synthesis of Benzonitriles and Their Heterocyclic Analogues

Influence of Lewis acids on the Diels–Alder reaction. II. Rearrangement of 1- and 1,4-substituted diethyl 7-oxabicyclo[2•2•1]2,5-heptadiene-2,3-dicarboxylate adducts to 4- and 4,6-substituted diethyl 3-hydroxyphthalates

Diels‐Alder‐Reaktionen I: Präparative Aspekte

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Chemistry of the 1,4-Diamino-1,3-butadines. IV. The Diels-Alder Reaction¹