0000000001302127
AUTHOR
Ferenc Miklós
Application of Furan as a Diene: Preparation of Condensed 1,3-Oxazines by Retro-Diels−Alder Reactions
(Di-exo-3-amino-7-oxabicyclo[2.2.1]hept-5-en-2-yl)methanol (3) was treated with oxo carboxylic acids [p-toluoylpropionic acid, cis- or trans-(p-toluoyl)cyclohexanecarboxylic acid, -benzoic acid or methanobenzocyclooctenecarboxylic acid] to furnish the oxanorbornene-fused pyrrolo[1,3]oxazine 4, the isoindolo[1,3]oxazines 5 and 6, and the methanobenzocyclooctenepyrrolo[1,3]oxazine 10, together with the retro-Diels−Alder products pyrrolooxazinone 7, oxazinoisoindolones 8 and 9, and oxazinopyrrolobenzocyclooctene 11. On reflux in chlorobenzene, furan was released from the oxanorbornene heterocycles 5 and 10 to give the retro-Diels−Alder products. The structures of the new compounds were establi…
Preparation and structure of pyrrolo[2,1-b]- and isoindolo[1,2-b][3,1]epoxyquinazolines
Abstract Various γ-oxocarboxylic acids [aroylpropionic acids, cis-2-(4-methylbenzoyl)cyclohexanecarboxylic acid, diendo-3-benzoylbicyclo[2.2.1] heptane-2-carboxylic acid, formylbenzoic acid, methanobenzenecyclooctencarboxylic acid and the cyclopentadiene adduct of 3-trans-(4-methylbenzoyl)acrylic acid] were reacted with diexo-3-aminomethyl-7-oxabicyclo[2.2.1]hept-5-en-2-ylamine 2 to result in condensed pyrroloepoxyquinazolines 3–10. The starting 2 retained the diexo configuration, but cis → trans isomerization took place when cis-2-(4-methylbenzoyl)cyclohexanecarboxylic acid was applied. The structures, including the ring annelations and the position of the aryl group on the new chiral cent…
Isomerization and Application of Aroylnorbornenecarboxylic Acids for Stereoselective Preparation of Heterocycles
When boiled in acidic or basic solution, diendo-3-aroylbicyclo[2.2.1]heptane-2-carboxylic acids (1 and la) isomerize to exo-3-aroylbicyclo[2.2.1]heptane-endo-2-carboxylic acids (2 and 2a). Similar endo→exo and even exo → endo isomerization of the aroyl group occurred when the Diels-Alder product containing a mixture of 3-exo-p-toluoylbicyclo[2.2.1 ]hept-5-ene-2-endo-carboxylic acid (4) and 3-endo-p-toluoylbicyclo[2.2.1]hept-5-ene-2-exo-carboxylic acid (5) was reacted with bifunctional reagents: o-aminothiophenol, 3-amino-1-propanol, 1,4-diaminobutane or diexo-3-hydroxymethylbicyclo[2.2.1]heptane-2-amine. All the reactions yielded mixtures of norbornene diendo- and diexo-fused heterocycles (…
Traceless chirality transfer from a norbornene β-amino acid to pyrimido[2,1-a]isoindole enantiomers
The synthesis of two enantiomeric pairs of pyrimidoisoindoles 9a, 9b and 10a, 10b is reported. During a domino ring-closure reaction, followed by cycloreversion, the chirality of diendo-(−)-(1R,2S,3R,4S)-3-aminobicyclo[2.2.1]hept-5-ene-2-carboxamide [(−)-1] was successfully transfered to heterocycles (+)-9a, (+)-10a, (−)-9b, (−)-10b and (−)-10c. peerReviewed
Preparation and Structures of Isoindolone- or Pyrimidone-Condensed Heterocycles Containing a Hydroxy Group on a Cyclohexane or Norbornane Moiety
With DL-valinol, 3-amino-1-propanol and o-aminothiophenol, aroyl(bi/tri)cyclic lactones 1 and 2 were cy- clized to isoindole- 4-6, 8, 9, pyrimidinone- 10 or thiazepine- 7 condensed heterocycles. The ketal lactone 3 furnished the benzthiazoloisoindole 9 and mixtures of epimeric hydroxyphthalazinoquinazolinones 11 and 12. The structures were es- tablished by means of 1 H and 13 C NMR spectroscopy and in some cases by X-ray crystallography.
Retro-Diels-Alder Protocol for the Synthesis of Pyrrolo[1,2-a]pyrimidine and Pyrimido[2,1-a]isoindole Enantiomers
A simple protocol was introduced to prepare several enantiomerically pure heterocycles by using (–)-(1R,2R,3S,4S)-3-aminonorbornene-2-carboxylic acid as a chiral auxiliary. The protocol is based on a domino ring-closure reaction, in which the relative configuration of the new asymmetric center is controlled by the stereochemistry of the amino acid, followed by a microwave-induced retro-Diels–Alder reaction.
Traceless chirality transfer from a norbornene β-amino acid to pyrimido[2,1-a]isoindole enantiomers
Abstract The synthesis of two enantiomeric pairs of pyrimidoisoindoles 9a, 9b and 10a, 10b is reported. During a domino ring-closure reaction, followed by cycloreversion, the chirality of diendo-(−)-(1R,2S,3R,4S)-3-aminobicyclo[2.2.1]hept-5-ene-2-carboxamide [(−)-1] was successfully transfered to heterocycles (+)-9a, (+)-10a, (−)-9b, (−)-10b and (−)-10c.
Stereocontrolled synthesis of five diastereomers of trimethyl 3-aminocyclopentane-1,2,4-tricarboxylates
Abstract The sterically controlled oxidative cleavage of N - protected di exo - and di endo -substituted norbornene β-amino acids/esters resulted in four trimethyl 3-aminocyclopentane-1,2,4-carboxylate diastereomers. The sodium methoxide mediated isomerization of the four diastereomers in all cases yielded the thermodynamically most stable all- trans stereoisomer as a single product.
Preparation and Structure of Diexo-Oxanorbornane-fused 1,3-Heterocycles
Via the reaction of diexo-oxanorbornanedicarboxylic anhydride with toluene, the diexo-aroylcarboxylic acid (3a) was prepared, which exists partly as the tautomeric lactol (3b). With bifunctional reagents, 3a yields fused heterocycles containing three-six rings. Thus, alkylenediamines result in imidazole- and 1,3-diazepine-fused oxygen- bridged isoindolones (6a,b), alkanolamines form the oxazole- and 1,3-oxazine-fused oxanorbornene derivatives (7a-c), and o-phenylenediamine undergoes cyclization to furnish the condensed benzimidazole (8). The reaction of 3a with diexo- aminonorbornanecarbohydrazide yields a pyrimidopyridazine containing six condensed rings (9). In a similar reaction with die…
CCDC 922681: Experimental Crystal Structure Determination
Related Article: Ferenc Miklós, István M. Mándity, Reijo Sillanpää, Ferenc Fülöp|2013|Tetrahedron Lett.|54|3769|doi:10.1016/j.tetlet.2013.05.009
CCDC 924270: Experimental Crystal Structure Determination
Related Article: Ferenc Miklós, Zita Tóth, Mikko M. Hänninen, Reijo Sillanpää, Enikő Forró and Ferenc Fülöp|2013|Eur.J.Org.Chem.|2013|4887|doi:10.1002/ejoc.201300452
CCDC 924268: Experimental Crystal Structure Determination
Related Article: Ferenc Miklós, Zita Tóth, Mikko M. Hänninen, Reijo Sillanpää, Enikő Forró and Ferenc Fülöp|2013|Eur.J.Org.Chem.|2013|4887|doi:10.1002/ejoc.201300452
CCDC 922680: Experimental Crystal Structure Determination
Related Article: Ferenc Miklós, István M. Mándity, Reijo Sillanpää, Ferenc Fülöp|2013|Tetrahedron Lett.|54|3769|doi:10.1016/j.tetlet.2013.05.009
CCDC 924269: Experimental Crystal Structure Determination
Related Article: Ferenc Miklós, Zita Tóth, Mikko M. Hänninen, Reijo Sillanpää, Enikő Forró and Ferenc Fülöp|2013|Eur.J.Org.Chem.|2013|4887|doi:10.1002/ejoc.201300452
CCDC 1964840: Experimental Crystal Structure Determination
Related Article: Ferenc Miklós, Kristof Bozó, Zsolt Galla, Matti Haukka, Ferenc Fülöp|2017|Tetrahedron:Asymm.|28|1401|doi:10.1016/j.tetasy.2017.07.006
CCDC 1964839: Experimental Crystal Structure Determination
Related Article: Ferenc Miklós, Kristof Bozó, Zsolt Galla, Matti Haukka, Ferenc Fülöp|2017|Tetrahedron:Asymm.|28|1401|doi:10.1016/j.tetasy.2017.07.006
CCDC 924267: Experimental Crystal Structure Determination
Related Article: Ferenc Miklós, Zita Tóth, Mikko M. Hänninen, Reijo Sillanpää, Enikő Forró and Ferenc Fülöp|2013|Eur.J.Org.Chem.|2013|4887|doi:10.1002/ejoc.201300452
CCDC 1964841: Experimental Crystal Structure Determination
Related Article: Ferenc Miklós, Kristof Bozó, Zsolt Galla, Matti Haukka, Ferenc Fülöp|2017|Tetrahedron:Asymm.|28|1401|doi:10.1016/j.tetasy.2017.07.006
CCDC 1964842: Experimental Crystal Structure Determination
Related Article: Ferenc Miklós, Kristof Bozó, Zsolt Galla, Matti Haukka, Ferenc Fülöp|2017|Tetrahedron:Asymm.|28|1401|doi:10.1016/j.tetasy.2017.07.006