Non-Biaryl Atropisomers in Organocatalysis
A new class of 6′‐hydroxy cinchona alkaloids, with a non‐biaryl atropisomeric functionalisation at position 5′ of the quinoline core can be prepared by an easy amination procedure. These are the first derivatives for which the principle of atropisomerism is engrafted in the classical core of the cin...
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| Vydané v: | Chemistry : a European journal Ročník 12; číslo 23; s. 6039 - 6052 |
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| Hlavní autori: | , , , , , |
| Médium: | Journal Article |
| Jazyk: | English |
| Vydavateľské údaje: |
Weinheim
WILEY-VCH Verlag
07.08.2006
WILEY‐VCH Verlag Wiley |
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| ISSN: | 0947-6539, 1521-3765 |
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| Abstract | A new class of 6′‐hydroxy cinchona alkaloids, with a non‐biaryl atropisomeric functionalisation at position 5′ of the quinoline core can be prepared by an easy amination procedure. These are the first derivatives for which the principle of atropisomerism is engrafted in the classical core of the cinchona alkaloids. The aminated cinchona alkaloids are effective organocatalysts for the Michael addition of β‐keto esters to acrolein and methyl vinyl ketone, in up to 93 % ee (ee=enantiomeric excess), as well as for the asymmetric Friedel–Crafts amination of a variety of 2‐naphthols, permitting the preparation of the latter in up to 98 % ee. The aminated 8‐amino‐2‐naphthol itself is the first chiral organocatalyst based on non‐biaryl atropisomerism. The two enantiomers of this chiral primary amine can be used for the direct α‐fluorination of α‐branched aldehydes. The fluorinated compounds can thereby be accessed in up to 90 % ee.
Friedel–Crafts aminations: Combine non‐biaryl atropisomerism and organocatalysis and a variety of reactions will be catalysed. These two concepts were combined in cinchona alkaloid derivatives and in chiral primary amines (see scheme). The atropisomeric compounds were then used as catalysts in Friedel–Crafts aminations (up to 98 % ee), in Michael additions (up to 93 % ee) and in fluorinations of α‐branched aldehydes (up to 90 % ee). |
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| AbstractList | A new class of 6′‐hydroxy cinchona alkaloids, with a non‐biaryl atropisomeric functionalisation at position 5′ of the quinoline core can be prepared by an easy amination procedure. These are the first derivatives for which the principle of atropisomerism is engrafted in the classical core of the cinchona alkaloids. The aminated cinchona alkaloids are effective organocatalysts for the Michael addition of β‐keto esters to acrolein and methyl vinyl ketone, in up to 93 % ee (ee=enantiomeric excess), as well as for the asymmetric Friedel–Crafts amination of a variety of 2‐naphthols, permitting the preparation of the latter in up to 98 % ee. The aminated 8‐amino‐2‐naphthol itself is the first chiral organocatalyst based on non‐biaryl atropisomerism. The two enantiomers of this chiral primary amine can be used for the direct α‐fluorination of α‐branched aldehydes. The fluorinated compounds can thereby be accessed in up to 90 % ee.
Friedel–Crafts aminations: Combine non‐biaryl atropisomerism and organocatalysis and a variety of reactions will be catalysed. These two concepts were combined in cinchona alkaloid derivatives and in chiral primary amines (see scheme). The atropisomeric compounds were then used as catalysts in Friedel–Crafts aminations (up to 98 % ee), in Michael additions (up to 93 % ee) and in fluorinations of α‐branched aldehydes (up to 90 % ee). A new class of 6'-hydroxy cinchona alkaloids, with a non-biaryl atropisomeric functionalisation at position 5' of the quinoline core can be prepared by an easy amination procedure. These are the first derivatives for which the principle of atropisomerism is engrafted in the classical core of the cinchona alkaloids. The aminated cinchona alkaloids are effective organocatalysts for the Michael addition of beta-keto esters to acrolein and methyl vinyl ketone, in up to 93 % ee (ee=enantiomeric excess), as well as for the asymmetric Friedel-Crafts amination of a variety of 2-naphthols, permitting the preparation of the latter in up to 98 % ee. The aminated 8-amino-2-naphthol itself is the first chiral organocatalyst based on non-biaryl atropisomerism. The two enantiomers of this chiral primary amine can be used for the direct alpha-fluorination of alpha-branched aldehydes. The fluorinated compounds can thereby be accessed in up to 90 % ee.A new class of 6'-hydroxy cinchona alkaloids, with a non-biaryl atropisomeric functionalisation at position 5' of the quinoline core can be prepared by an easy amination procedure. These are the first derivatives for which the principle of atropisomerism is engrafted in the classical core of the cinchona alkaloids. The aminated cinchona alkaloids are effective organocatalysts for the Michael addition of beta-keto esters to acrolein and methyl vinyl ketone, in up to 93 % ee (ee=enantiomeric excess), as well as for the asymmetric Friedel-Crafts amination of a variety of 2-naphthols, permitting the preparation of the latter in up to 98 % ee. The aminated 8-amino-2-naphthol itself is the first chiral organocatalyst based on non-biaryl atropisomerism. The two enantiomers of this chiral primary amine can be used for the direct alpha-fluorination of alpha-branched aldehydes. The fluorinated compounds can thereby be accessed in up to 90 % ee. A new class of 6′‐hydroxy cinchona alkaloids, with a non‐biaryl atropisomeric functionalisation at position 5′ of the quinoline core can be prepared by an easy amination procedure. These are the first derivatives for which the principle of atropisomerism is engrafted in the classical core of the cinchona alkaloids. The aminated cinchona alkaloids are effective organocatalysts for the Michael addition of β‐keto esters to acrolein and methyl vinyl ketone, in up to 93 % ee ( ee =enantiomeric excess), as well as for the asymmetric Friedel–Crafts amination of a variety of 2‐naphthols, permitting the preparation of the latter in up to 98 % ee . The aminated 8‐amino‐2‐naphthol itself is the first chiral organocatalyst based on non‐biaryl atropisomerism. The two enantiomers of this chiral primary amine can be used for the direct α‐fluorination of α‐branched aldehydes. The fluorinated compounds can thereby be accessed in up to 90 % ee . A new class of 6'-hydroxy cinchona alkaloids, with a non-biaryl atropisomeric functionalisation at position 5' of the quinoline core can be prepared by an easy amination procedure. These are the first derivatives for which the principle of atropisomerism is engrafted in the classical core of the cinchona alkaloids. The aminated cinchona alkaloids are effective organocatalysts for the Michael addition of beta-keto esters to acrolein and methyl vinyl ketone, in up to 93 % ee (ee=enantiomeric excess), as well as for the asymmetric Friedel-Crafts amination of a variety of 2-naphthols, permitting the preparation of the latter in up to 98 % ee. The aminated 8-amino-2-naphthol itself is the first chiral organocatalyst based on non-biaryl atropisomerism. The two enantiomers of this chiral primary amine can be used for the direct alpha-fluorination of alpha-branched aldehydes. The fluorinated compounds can thereby be accessed in up to 90 % ee. A new class of 6-hydroxy cinchona alkaloids, with a non-biaryl atropisomeric functionalisation at position 5' of the quinoline core can be prepared by an easy amination procedure. These are the first derivatives for which the principle of atropisomerism is engrafted in the classical core of the cinchona alkaloids. The aminated cinchona alkaloids are effective organocatalysts for the Michael addition of beta-keto esters to acrolein and methyl vinyl ketone, in up to 93% ee (ee=enantiomeric excess), as well as for the asymmetric Friedel-Crafts amination of a variety of 2-naphthols, permitting the preparation of the latter in up to 98% ee. The aminated 8-amino-2-naphthol itself is the first chiral organocatalyst based on non-biaryl atropisomerism. The two enantiomers of this chiral primary amine can be used for the direct a-fluorination of a-branched aldehydes. The fluorinated compounds can thereby be accessed in up to 90% ee. |
| Author | Bella, Marco Niess, Barbara Jørgensen, Karl Anker Brandes, Sebastian Overgaard, Jacob Prieto, Auxiliadora |
| Author_xml | – sequence: 1 givenname: Sebastian surname: Brandes fullname: Brandes, Sebastian organization: The Danish National Research Foundation, Center for Catalysis, Department of Chemistry, Aarhus University, 8000 Aarhus C, Denmark, Fax: (+45) 8619-6199 – sequence: 2 givenname: Barbara surname: Niess fullname: Niess, Barbara organization: The Danish National Research Foundation, Center for Catalysis, Department of Chemistry, Aarhus University, 8000 Aarhus C, Denmark, Fax: (+45) 8619-6199 – sequence: 3 givenname: Marco surname: Bella fullname: Bella, Marco organization: The Danish National Research Foundation, Center for Catalysis, Department of Chemistry, Aarhus University, 8000 Aarhus C, Denmark, Fax: (+45) 8619-6199 – sequence: 4 givenname: Auxiliadora surname: Prieto fullname: Prieto, Auxiliadora organization: The Danish National Research Foundation, Center for Catalysis, Department of Chemistry, Aarhus University, 8000 Aarhus C, Denmark, Fax: (+45) 8619-6199 – sequence: 5 givenname: Jacob surname: Overgaard fullname: Overgaard, Jacob organization: The Danish National Research Foundation, Center for Catalysis, Department of Chemistry, Aarhus University, 8000 Aarhus C, Denmark, Fax: (+45) 8619-6199 – sequence: 6 givenname: Karl Anker surname: Jørgensen fullname: Jørgensen, Karl Anker email: kaj@chem.au.dk organization: The Danish National Research Foundation, Center for Catalysis, Department of Chemistry, Aarhus University, 8000 Aarhus C, Denmark, Fax: (+45) 8619-6199 |
| BackLink | https://www.ncbi.nlm.nih.gov/pubmed/16789058$$D View this record in MEDLINE/PubMed |
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| Copyright | Copyright © 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim |
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| Issue | 23 |
| Keywords | Michael addition fluorination BAYLIS-HILLMAN REACTION QUATERNARY STEREOCENTERS EFFICIENT SYNTHESIS asymmetric catalysis AXIALLY CHIRAL ANILIDES atropisomerism CINCHONA ALKALOIDS ENANTIOSELECTIVE CONJUGATE ADDITION ASYMMETRIC MICHAEL REACTIONS amination STEREOSELECTIVE-SYNTHESIS ALPHA-FLUORINATION CARBON-NITROGEN BONDS |
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| PublicationCentury | 2000 |
| PublicationDate | August 7, 2006 |
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| PublicationTitle | Chemistry : a European journal |
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(e_1_2_5_28_2) 2000 e_1_2_5_80_2 e_1_2_5_61_2 e_1_2_5_84_2 e_1_2_5_38_2 e_1_2_5_155_2 e_1_2_5_15_2 e_1_2_5_57_2 e_1_2_5_7_2 e_1_2_5_34_2 e_1_2_5_113_2 e_1_2_5_151_2 e_1_2_5_11_2 e_1_2_5_53_2 e_1_2_5_132_2 e_1_2_5_3_2 e_1_2_5_76_2 e_1_2_5_117_2 e_1_2_5_76_3 e_1_2_5_99_2 e_1_2_5_136_2 e_1_2_5_159_2 e_1_2_5_19_2 e_1_2_5_91_2 e_1_2_5_72_2 e_1_2_5_95_2 e_1_2_5_26_2 e_1_2_5_49_2 e_1_2_5_146_2 e_1_2_5_22_2 e_1_2_5_45_2 e_1_2_5_123_2 e_1_2_5_100_2 e_1_2_5_64_2 e_1_2_5_87_2 e_1_2_5_127_2 e_1_2_5_68_2 e_1_2_5_108_2 e_1_2_5_60_2 e_1_2_5_60_3 e_1_2_5_83_2 e_1_2_5_41_2 e_1_2_5_14_2 e_1_2_5_37_2 e_1_2_5_131_2 e_1_2_5_154_2 e_1_2_5_8_2 e_1_2_5_10_2 e_1_2_5_33_2 e_1_2_5_56_2 e_1_2_5_112_2 e_1_2_5_135_2 e_1_2_5_150_2 e_1_2_5_4_2 e_1_2_5_10_3 e_1_2_5_75_2 e_1_2_5_98_2 e_1_2_5_116_2 e_1_2_5_139_2 e_1_2_5_75_3 e_1_2_5_18_2 e_1_2_5_79_2 e_1_2_5_158_2 e_1_2_5_90_2 e_1_2_5_71_2 e_1_2_5_94_2 e_1_2_5_94_3 e_1_2_5_52_2 Eliel E. L. 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| Snippet | A new class of 6′‐hydroxy cinchona alkaloids, with a non‐biaryl atropisomeric functionalisation at position 5′ of the quinoline core can be prepared by an easy... A new class of 6-hydroxy cinchona alkaloids, with a non-biaryl atropisomeric functionalisation at position 5' of the quinoline core can be prepared by an easy... A new class of 6'-hydroxy cinchona alkaloids, with a non-biaryl atropisomeric functionalisation at position 5' of the quinoline core can be prepared by an easy... |
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| SubjectTerms | amination asymmetric catalysis atropisomerism Chemistry Chemistry, Multidisciplinary fluorination Michael addition Physical Sciences Science & Technology |
| Title | Non-Biaryl Atropisomers in Organocatalysis |
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