Copper-Catalyzed Oxidative Amination of Benzoxazoles via C−H and C−N Bond Activation: A New Strategy for Using Tertiary Amines as Nitrogen Group Sources
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An efficient and conceptually new method for oxidative amination of azoles with tertiary amines via copper-catalyzed C-H and C-N bond activation has been developed. This protocol can be performed in the absence of external base and only requires atmospheric oxygen as oxidant. The catalyst system is very simple and efficient, which opens a new way for using tertiary amines as nitrogen group sources for C-N bond formation reactions.Keywords:
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Abstract A novel and efficient Rh‐catalyzed intermolecular C–H amination of heteroarylarenes with aryl azides has been developed. This procedure does not require an oxidant, releases N 2 as the only byproduct, and provides an efficient approach to diarylamines with broad functional‐group tolerance.
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Abstract Introducing the primary amino group into aromatic ring is one of the most important study issues in organic chemistry, particularly for the pharmaceuticals and agrochemicals chemistry. Herein, we describe a photoinduced direct C−H amination of arenes with ammonia via the site‐selective C−H thianthrenation that forms a new C−N bond with excellent regioselectivity. The reaction is carried out under mild conditions, and with a wide range of functional group tolerance, such as sensitive −Cl, −Br, and −OH groups which are poorly tolerated in conventional approaches. Moreover, the synthetic utility of our amination protocol has been confirmed through late‐stage modification and gram‐scale synthesis of complex drug‐like molecules.
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A highly regioselective protocol for intermolecular thiocyanation-amination of alkynes by N-thiocyano-dibenzenesulfonimide (NTSI) as the SCN and nitrogen sources has been developed. A C–S bond and C–N bond are simultaneously constructed in only one step. The reaction under simple mild conditions features a broad substrate scope, atom economy, high yields (up to 94%), and excellent functional group tolerance.
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Nitrogen atom
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The transient directing group promoted C(sp2)–H functionalization of benzaldehydes with anthranils by a cationic rhodium(III) catalyst is described. Notably, anthranils have been used as both transient directing groups and amination sources to afford 2-acyl acridines through direct C–H amination followed by acid-mediated cyclization. A range of substrate scopes and functional group tolerance were observed.
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We report herein a copper-mediated ortho-C–H amination of anilines using oxalamide as the directing group and DMF as the amination reagent. This protocol tolerates various functional groups and shows good heterocyclic compatibility. Late-stage dimethylamination of drugs demonstrated the synthetic practicality of the protocol. Mechanistic experiments indicate that a radical pathway may be involved in the reaction.
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