Enantioconvergent Cu-Catalyzed Intramolecular C-C Coupling at Boron-Bound C(sp3) Atoms of α-Aminoalkylboronates Using a C1-Symmetrical 2,2'-Bipyridyl Ligand Attached to a Helically Chiral Macromolecular Scaffold
Enantioconvergent intramolecular coupling of α-(2-bromobenzoylamino)benzylboronic esters was achieved using a copper catalyst having helically chiral macromolecular bipyridyl ligand, PQXbpy. Racemic α-(2-bromobenzoylamino)benzylboronic esters were converted into (R)-configured 3-arylisoindolinones with high enantiopurity using right-handed helical PQXbpy as a chiral ligand in a toluene/CHCl3 mixed solvent. When enantiopure (R)- and (S)-configured boronates were separately reacted under the same reaction conditions, both afforded (R)-configured products through formal stereoinvertive and stereoretentive processes, respectively. From these results, a mechanism involving deracemization of organocopper intermediates in the presence of PQXbpy is assumed. PQXbpy switched its helical sense to left-handed when a toluene/1,1,2-trichloroethane mixed solvent was used, resulting in the formation of the corresponding (S)-products from the racemic starting material.
Medienart: |
E-Artikel |
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Erscheinungsjahr: |
2020 |
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Erschienen: |
2020 |
Enthalten in: |
Zur Gesamtaufnahme - volume:142 |
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Enthalten in: |
Journal of the American Chemical Society - 142(2020), 43 vom: 28. Okt., Seite 18317-18323 |
Sprache: |
Englisch |
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Beteiligte Personen: |
Yoshinaga, Yukako [VerfasserIn] |
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Anmerkungen: |
Date Completed 05.02.2021 Date Revised 05.02.2021 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
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doi: |
10.1021/jacs.0c09080 |
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funding: |
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Förderinstitution / Projekttitel: |
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PPN (Katalog-ID): |
NLM316334774 |
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245 | 1 | 0 | |a Enantioconvergent Cu-Catalyzed Intramolecular C-C Coupling at Boron-Bound C(sp3) Atoms of α-Aminoalkylboronates Using a C1-Symmetrical 2,2'-Bipyridyl Ligand Attached to a Helically Chiral Macromolecular Scaffold |
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500 | |a published: Print-Electronic | ||
500 | |a Citation Status PubMed-not-MEDLINE | ||
520 | |a Enantioconvergent intramolecular coupling of α-(2-bromobenzoylamino)benzylboronic esters was achieved using a copper catalyst having helically chiral macromolecular bipyridyl ligand, PQXbpy. Racemic α-(2-bromobenzoylamino)benzylboronic esters were converted into (R)-configured 3-arylisoindolinones with high enantiopurity using right-handed helical PQXbpy as a chiral ligand in a toluene/CHCl3 mixed solvent. When enantiopure (R)- and (S)-configured boronates were separately reacted under the same reaction conditions, both afforded (R)-configured products through formal stereoinvertive and stereoretentive processes, respectively. From these results, a mechanism involving deracemization of organocopper intermediates in the presence of PQXbpy is assumed. PQXbpy switched its helical sense to left-handed when a toluene/1,1,2-trichloroethane mixed solvent was used, resulting in the formation of the corresponding (S)-products from the racemic starting material | ||
650 | 4 | |a Journal Article | |
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700 | 1 | |a Suginome, Michinori |e verfasserin |4 aut | |
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