author_facet Szatmári, István
Belasri, Khadija
Heydenreich, Matthias
Koch, Andreas
Kleinpeter, Erich
Fülöp, Ferenc
Szatmári, István
Belasri, Khadija
Heydenreich, Matthias
Koch, Andreas
Kleinpeter, Erich
Fülöp, Ferenc
author Szatmári, István
Belasri, Khadija
Heydenreich, Matthias
Koch, Andreas
Kleinpeter, Erich
Fülöp, Ferenc
spellingShingle Szatmári, István
Belasri, Khadija
Heydenreich, Matthias
Koch, Andreas
Kleinpeter, Erich
Fülöp, Ferenc
ChemistryOpen
Ortho‐Quinone Methide Driven Synthesis of New O,N‐ or N,N‐Heterocycles
General Chemistry
author_sort szatmári, istván
spelling Szatmári, István Belasri, Khadija Heydenreich, Matthias Koch, Andreas Kleinpeter, Erich Fülöp, Ferenc 2191-1363 2191-1363 Wiley General Chemistry http://dx.doi.org/10.1002/open.201900150 <jats:title>Abstract</jats:title><jats:p>To synthesize functionalized Mannich bases that can serve two different types of <jats:italic>ortho</jats:italic>‐quinone methide (<jats:italic>o</jats:italic>‐QM) intermediates, 2‐naphthol and 6‐hydroxyquinoline were reacted with salicylic aldehyde in the presence of morpholine. The Mannich bases that can form <jats:italic>o</jats:italic>‐QM and <jats:italic>aza</jats:italic>‐<jats:italic>o</jats:italic>‐QM were also synthesized by mixing 2‐naphthol, 2‐nitrobenzaldehyde, and morpholine followed by reduction of the nitro group. The highly functionalized aminonaphthol derivatives were then tested in [4+2] cycloaddition with different cyclic imines. The reaction proved to be both regio‐ and diastereoselective. In all cases, only one reaction product was obtained. Detailed structural analyses of the new polyheterocycles as well as conformational studies including DFT modelling were performed. The relative stability of <jats:italic>o</jats:italic>‐QMs/<jats:italic>aza‐o</jats:italic>‐QM were also calculated, and the regioselectivity of the reactions could be explained only when the cycloaddition started from aminodiol <jats:bold>4</jats:bold>. It was summarized that starting from diaminonaphthol <jats:bold>25</jats:bold>, the regioselectivity of the reaction is driven by the higher nucleophilicity of the amino group compared with the hydroxy group. 12H‐benzo[a]xanthen‐12‐one (<jats:bold>11</jats:bold>), formed via <jats:italic>o</jats:italic>‐QM formation, was isolated as a side product. The proton NMR spectrum of <jats:bold>11</jats:bold> proved to be very unique from NMR point of view. The reason for the extreme low‐field position of proton H‐1 could be accounted for by theoretical calculation of structure and spatial magnetic properties of the compound in combination of ring current effects of the aromatic moieties and steric compression within the heavily hindered H(1)‐C(1)‐C(12b)‐C(12a)‐C(12)=O structural fragment.</jats:p> <i>Ortho</i>‐Quinone Methide Driven Synthesis of New <i>O</i>,<i>N</i>‐ or <i>N</i>,<i>N</i>‐Heterocycles ChemistryOpen
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title Ortho‐Quinone Methide Driven Synthesis of New O,N‐ or N,N‐Heterocycles
title_unstemmed Ortho‐Quinone Methide Driven Synthesis of New O,N‐ or N,N‐Heterocycles
title_full Ortho‐Quinone Methide Driven Synthesis of New O,N‐ or N,N‐Heterocycles
title_fullStr Ortho‐Quinone Methide Driven Synthesis of New O,N‐ or N,N‐Heterocycles
title_full_unstemmed Ortho‐Quinone Methide Driven Synthesis of New O,N‐ or N,N‐Heterocycles
title_short Ortho‐Quinone Methide Driven Synthesis of New O,N‐ or N,N‐Heterocycles
title_sort <i>ortho</i>‐quinone methide driven synthesis of new <i>o</i>,<i>n</i>‐ or <i>n</i>,<i>n</i>‐heterocycles
topic General Chemistry
url http://dx.doi.org/10.1002/open.201900150
publishDate 2019
physical 961-971
description <jats:title>Abstract</jats:title><jats:p>To synthesize functionalized Mannich bases that can serve two different types of <jats:italic>ortho</jats:italic>‐quinone methide (<jats:italic>o</jats:italic>‐QM) intermediates, 2‐naphthol and 6‐hydroxyquinoline were reacted with salicylic aldehyde in the presence of morpholine. The Mannich bases that can form <jats:italic>o</jats:italic>‐QM and <jats:italic>aza</jats:italic>‐<jats:italic>o</jats:italic>‐QM were also synthesized by mixing 2‐naphthol, 2‐nitrobenzaldehyde, and morpholine followed by reduction of the nitro group. The highly functionalized aminonaphthol derivatives were then tested in [4+2] cycloaddition with different cyclic imines. The reaction proved to be both regio‐ and diastereoselective. In all cases, only one reaction product was obtained. Detailed structural analyses of the new polyheterocycles as well as conformational studies including DFT modelling were performed. The relative stability of <jats:italic>o</jats:italic>‐QMs/<jats:italic>aza‐o</jats:italic>‐QM were also calculated, and the regioselectivity of the reactions could be explained only when the cycloaddition started from aminodiol <jats:bold>4</jats:bold>. It was summarized that starting from diaminonaphthol <jats:bold>25</jats:bold>, the regioselectivity of the reaction is driven by the higher nucleophilicity of the amino group compared with the hydroxy group. 12H‐benzo[a]xanthen‐12‐one (<jats:bold>11</jats:bold>), formed via <jats:italic>o</jats:italic>‐QM formation, was isolated as a side product. The proton NMR spectrum of <jats:bold>11</jats:bold> proved to be very unique from NMR point of view. The reason for the extreme low‐field position of proton H‐1 could be accounted for by theoretical calculation of structure and spatial magnetic properties of the compound in combination of ring current effects of the aromatic moieties and steric compression within the heavily hindered H(1)‐C(1)‐C(12b)‐C(12a)‐C(12)=O structural fragment.</jats:p>
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author Szatmári, István, Belasri, Khadija, Heydenreich, Matthias, Koch, Andreas, Kleinpeter, Erich, Fülöp, Ferenc
author_facet Szatmári, István, Belasri, Khadija, Heydenreich, Matthias, Koch, Andreas, Kleinpeter, Erich, Fülöp, Ferenc, Szatmári, István, Belasri, Khadija, Heydenreich, Matthias, Koch, Andreas, Kleinpeter, Erich, Fülöp, Ferenc
author_sort szatmári, istván
container_issue 7
container_start_page 961
container_title ChemistryOpen
container_volume 8
description <jats:title>Abstract</jats:title><jats:p>To synthesize functionalized Mannich bases that can serve two different types of <jats:italic>ortho</jats:italic>‐quinone methide (<jats:italic>o</jats:italic>‐QM) intermediates, 2‐naphthol and 6‐hydroxyquinoline were reacted with salicylic aldehyde in the presence of morpholine. The Mannich bases that can form <jats:italic>o</jats:italic>‐QM and <jats:italic>aza</jats:italic>‐<jats:italic>o</jats:italic>‐QM were also synthesized by mixing 2‐naphthol, 2‐nitrobenzaldehyde, and morpholine followed by reduction of the nitro group. The highly functionalized aminonaphthol derivatives were then tested in [4+2] cycloaddition with different cyclic imines. The reaction proved to be both regio‐ and diastereoselective. In all cases, only one reaction product was obtained. Detailed structural analyses of the new polyheterocycles as well as conformational studies including DFT modelling were performed. The relative stability of <jats:italic>o</jats:italic>‐QMs/<jats:italic>aza‐o</jats:italic>‐QM were also calculated, and the regioselectivity of the reactions could be explained only when the cycloaddition started from aminodiol <jats:bold>4</jats:bold>. It was summarized that starting from diaminonaphthol <jats:bold>25</jats:bold>, the regioselectivity of the reaction is driven by the higher nucleophilicity of the amino group compared with the hydroxy group. 12H‐benzo[a]xanthen‐12‐one (<jats:bold>11</jats:bold>), formed via <jats:italic>o</jats:italic>‐QM formation, was isolated as a side product. The proton NMR spectrum of <jats:bold>11</jats:bold> proved to be very unique from NMR point of view. The reason for the extreme low‐field position of proton H‐1 could be accounted for by theoretical calculation of structure and spatial magnetic properties of the compound in combination of ring current effects of the aromatic moieties and steric compression within the heavily hindered H(1)‐C(1)‐C(12b)‐C(12a)‐C(12)=O structural fragment.</jats:p>
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spelling Szatmári, István Belasri, Khadija Heydenreich, Matthias Koch, Andreas Kleinpeter, Erich Fülöp, Ferenc 2191-1363 2191-1363 Wiley General Chemistry http://dx.doi.org/10.1002/open.201900150 <jats:title>Abstract</jats:title><jats:p>To synthesize functionalized Mannich bases that can serve two different types of <jats:italic>ortho</jats:italic>‐quinone methide (<jats:italic>o</jats:italic>‐QM) intermediates, 2‐naphthol and 6‐hydroxyquinoline were reacted with salicylic aldehyde in the presence of morpholine. The Mannich bases that can form <jats:italic>o</jats:italic>‐QM and <jats:italic>aza</jats:italic>‐<jats:italic>o</jats:italic>‐QM were also synthesized by mixing 2‐naphthol, 2‐nitrobenzaldehyde, and morpholine followed by reduction of the nitro group. The highly functionalized aminonaphthol derivatives were then tested in [4+2] cycloaddition with different cyclic imines. The reaction proved to be both regio‐ and diastereoselective. In all cases, only one reaction product was obtained. Detailed structural analyses of the new polyheterocycles as well as conformational studies including DFT modelling were performed. The relative stability of <jats:italic>o</jats:italic>‐QMs/<jats:italic>aza‐o</jats:italic>‐QM were also calculated, and the regioselectivity of the reactions could be explained only when the cycloaddition started from aminodiol <jats:bold>4</jats:bold>. It was summarized that starting from diaminonaphthol <jats:bold>25</jats:bold>, the regioselectivity of the reaction is driven by the higher nucleophilicity of the amino group compared with the hydroxy group. 12H‐benzo[a]xanthen‐12‐one (<jats:bold>11</jats:bold>), formed via <jats:italic>o</jats:italic>‐QM formation, was isolated as a side product. The proton NMR spectrum of <jats:bold>11</jats:bold> proved to be very unique from NMR point of view. The reason for the extreme low‐field position of proton H‐1 could be accounted for by theoretical calculation of structure and spatial magnetic properties of the compound in combination of ring current effects of the aromatic moieties and steric compression within the heavily hindered H(1)‐C(1)‐C(12b)‐C(12a)‐C(12)=O structural fragment.</jats:p> <i>Ortho</i>‐Quinone Methide Driven Synthesis of New <i>O</i>,<i>N</i>‐ or <i>N</i>,<i>N</i>‐Heterocycles ChemistryOpen
spellingShingle Szatmári, István, Belasri, Khadija, Heydenreich, Matthias, Koch, Andreas, Kleinpeter, Erich, Fülöp, Ferenc, ChemistryOpen, Ortho‐Quinone Methide Driven Synthesis of New O,N‐ or N,N‐Heterocycles, General Chemistry
title Ortho‐Quinone Methide Driven Synthesis of New O,N‐ or N,N‐Heterocycles
title_full Ortho‐Quinone Methide Driven Synthesis of New O,N‐ or N,N‐Heterocycles
title_fullStr Ortho‐Quinone Methide Driven Synthesis of New O,N‐ or N,N‐Heterocycles
title_full_unstemmed Ortho‐Quinone Methide Driven Synthesis of New O,N‐ or N,N‐Heterocycles
title_short Ortho‐Quinone Methide Driven Synthesis of New O,N‐ or N,N‐Heterocycles
title_sort <i>ortho</i>‐quinone methide driven synthesis of new <i>o</i>,<i>n</i>‐ or <i>n</i>,<i>n</i>‐heterocycles
title_unstemmed Ortho‐Quinone Methide Driven Synthesis of New O,N‐ or N,N‐Heterocycles
topic General Chemistry
url http://dx.doi.org/10.1002/open.201900150