251095-04-2

Upstream product

• 34243-82-8 1-bromo-2-oxo-cyclohexanecarboxylic acid ethyl ester 
• 1655-07-8 ethyl 2-oxocyclohexane carboxylate 

Downstream Products

• 38167-88-3 7-carboethoxy-tetrahydro-2(3H)-azepinone 
• 1361979-11-4 ethyl 2-oxo-1-(4-phenyl-1H-1,2,3-triazol-1-yl)cyclohexane-1-carboxylate 

Relevant academic research and scientific papers

Guanidinium iodide/urea hydrogen peroxide-catalyzed azidation of β-dicarbonyl compounds with trimethylsilyl azide

We present an efficient synthesis of α-azido-β-dicarbonyl compounds from β-dicarbonyl compounds and trimethylsilyl azide, catalyzed by guanidinium hypoiodite. The reaction can be run in air at ambient temperature (up to 40?°C) and is not sensitive to moisture. The substrate scope is broad, including cyclic and linear β-dicarbonyl compounds, and the α-azide products are obtained in 55%–99% yield.

Termination of Mn(III)-based oxidative cyclizations by trapping with azide

The radicals formed in Mn(III)-based oxidative free-radical cyclizations of β-keto esters and malonate esters can be trapped with sodium azide and Mn(III) to give cyclic and bicyclic azides in 30-80% yield. Reduction of the azide gives bi- and tricyclic l

Iron-Catalyzed Acyl Migration of Tertiary α-Azidyl Ketones: Synthetic Approach toward Enamides and Isoquinolones

This paper reports that tertiary α-azidyl phenyl ketones can be transformed into enamides by treatment with FeBr2 at elevated temperature in DMF. The reaction proceeds via 1,2-benzoyl migration from α-carbon to the nitrogen atom, accompanied by expulsion of a nitrogen molecule. This protocol is suitable for the synthesis of N-(cyclopent-1-en-1-yl)benzamides, N-(cyclohex-1-en-1-yl)benzamides, and N-benzoyl-α-methyl enamines and provides a convenient approach toward isoquinolones.

Unified strategy for Iodine(III)-Mediated Halogenation and azidation of 1,3-Dicarbonyl compounds

A mild and rapid (diacetoxyiodo)benzene-mediated formal electrophilic a-azidation of 1,3-dicarbonyl compounds using commercially available Bu 4NN3 as the azide source is reported. The reaction conditions employed are based on optimization studies conducted on the analogous halogenations with Et4NX (X = Cl, Br, I).

Practical azidation of 1,3-dicarbonyls

An operationally simple, direct azidation of 1,3-dicarbonyl compounds has been developed. The reaction proceeds readily under ambient conditions using sodium azide and an iodine-based oxidant such as I2 or 2-iodoxybenzoic acid (IBX)-SO3K/NaI. In particular, the latter method, as a new and well-balanced oxidizing agent, shows excellent functional group tolerance and substrate scope and thus allows access to a variety of tertiary 2-azido and 2,2-bisazido 1,3-dicarbonyl compounds that would be more difficult to access by using traditional methods. Because the azide-containing products easily undergo 1,3-dipolar cycloaddition with alkynes, our report represents a novel route to analogues of sensitive complex molecules. Click into place! An operationally simple, direct azidation of 1,3-dicarbonyl compounds has been developed (see scheme). The reaction proceeds readily under ambient conditions using sodium azide and an iodine-based oxidant, such as I2 or 2-iodoxybenzoic acid (IBX)-SO3K/NaI. The oxidative methods show excellent functional-group tolerance and substrate scope and thus allow access to a variety of tertiary 2-azido and 2,2-bisazido 1,3-dicarbonyl compounds. Copyright

Radical Chain Reactions of α-Azido-β-keto Esters with Tributyltin Hydride. a Novel Entry to Amides and Lactams through Regiospecific Nitrogen Insertion

A variety of acyclic and carbocyclic α-azido-β-keto esters have been readily prepared from the parent dicarbonyl compounds, and their radical chain reactions with tributyltin hydride have been investigated. These reactions normally result in efficient production of alkoxycarbonyl-substituted amides and lactams and thence provide a new, useful method for regiospecific nitrogen insertion of keto ester compounds. The likely mechanism entails initial addition of tributylstannyl radical to the azido moiety to give a stannylaminyl radical, which readily undergoes intramolecular three-membered cyclization onto the ketone group to form an alkoxyl radical. The alkoxyl radical then undergoes regiospecific β-scission to form a stable ring-opened radical that is eventually reduced by tributyltin hydride to propagate the chain. With certain substrates, concomitant deazidation occurs to an important extent. This process, which is unusually observed in radical reactions of alkyl azides, is ascribed to addition of the stannyl radical to the terminal azido nitrogen; subsequent fragmentation of the ensuing 1,3-triazenyl adduct gives stannyl azide and a deazidated alkyl radical, resonance-stabilized by the adjacent carbonyl groups. The radical reactions of 2-azido-2-(ethoxycarbonyl)-1-tetralone with allyltributylstannane and allyltriphenylstannane have also been investigated with the (missed) aim to achieve nitrogen insertion and concomitant allylation.