Intramolecular Amido Transfer Leading to Structurally Diverse Nitrogen-Containing Macrocycles
Heejeong Kim
Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon, 34141 Republic of Korea
Center for Catalytic Hydrocarbon Functionalization, Institute for Basic Science (IBS), Daejeon, 34141 Republic of Korea
Search for more papers by this authorCorresponding Author
Prof. Dr. Sukbok Chang
Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon, 34141 Republic of Korea
Center for Catalytic Hydrocarbon Functionalization, Institute for Basic Science (IBS), Daejeon, 34141 Republic of Korea
Search for more papers by this authorHeejeong Kim
Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon, 34141 Republic of Korea
Center for Catalytic Hydrocarbon Functionalization, Institute for Basic Science (IBS), Daejeon, 34141 Republic of Korea
Search for more papers by this authorCorresponding Author
Prof. Dr. Sukbok Chang
Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon, 34141 Republic of Korea
Center for Catalytic Hydrocarbon Functionalization, Institute for Basic Science (IBS), Daejeon, 34141 Republic of Korea
Search for more papers by this authorGraphical Abstract
Azamacrocycles: A rhodium-catalyzed inner-sphere intramolecular C−H amination of tailormade acetophenone ketoximes tethered with either aryl or alkyl azides furnishes azamacrocyclic compounds with up to 36-membered rings. While substrates bearing aryl azides underwent a monomeric ring formation in high yields, a dimeric double cyclization took place exclusively with alkyl-azide-tethered ketoximes.
Abstract
Reported herein is the development of rhodium-catalyzed intramolecular amido transfer as an efficient route to nitrogen-containing macrocycles starting from acetophenone ketoximes tethered with either aryl or alkyl azides. Facile generation of rhodacycles and metal imido intermediates was the key to success in this mechanistic scaffold to represent the first example of an intramolecular inner-sphere C−H amination. While substrates bearing aryl azides underwent a monomeric ring formation in high yields, a dimeric double cyclization took place exclusively with alkyl-azide-tethered ketoximes, thus affording up to 36-membered azamacrocyclic products.
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