22815-57-2

Upstream product

• 924-44-7 glyoxylic acid ethyl ester 
• 100-01-6 4-nitro-aniline 
• 100-15-2 N-methyl(p-nitroaniline) 
• 109-94-4 formic acid ethyl ester 

Downstream Products

• 1427299-87-3 ethyl 3,3-dimethyl-2-((4-nitrophenyl)amino)pent-4-enoate 
• 93-89-0 benzoic acid ethyl ester 
• 1400897-67-7 (S)-ethyl 2-(4-nitrophenylamino)-2-phenylacetate 
• 1330785-23-3 ethyl 2-benzamido-2-(4-nitrophenylamino)acetate 

Relevant academic research and scientific papers

Glyoxalate-derived aldimines in cycloaddition reactions with olefins

The reaction of aldimine 1a, derived from ethyl glyoxalate, with activated dienophiles, such as styrene and indene, gave the tetrahydro-1,5-naphthyridine derivatives 3 with regio- and stereoselective control of three stereocenters through a [4+2] cycloaddition process via endo transition states. However, when aldimine 1a was used in the reaction with strained olefins, such as norbornene or dicyclopentadiene, the corresponding [4+2] and [2+2] cycloadducts were obtained, through exclusive exo π-facial stereoselective cycloaddition. The addition of a second strained C=C bond in the olefin, such as norbornadiene, increased the multifunctional character of the olefin and a mixture of the corresponding exo [4+2] 11a and exo [2+2] 12a cycloadducts, as well as the corresponding HOMO cycloadduct 13a, was obtained. Reaction between norbornadiene and aldimines derived from p-nitro- and o,p-dinitroanilines and ethyl glyoxalate gave exo [4+2] cycloadducts 11b,c, HOMO cycloadducts 13b,c and α-amino γ-lactones 15b,c. A mechanistic explanation for the formation of the new products is suggested. Glyoxalate-derived aldimines react with styrene and indene to give endo [4+2] cycloadducts and with strained olefins to afford both exo [4+2] and [2+2] cycloadducts. The reaction with norbornadiene gives a mixture of exo [4+2] and [2+2] cycloadducts and the HOMO [2+2+2] cycloadduct, while the reaction of aldimines derived from nitroanilines with norbornadiene gives exo [4+2] and HOMO [2+2+2] cycloadducts and α-amino γ-lactones.

An unusual 1,2-aryl shift in palladium-catalyzed cross-coupling ethoxycarbonylation of arylboronic acids with α-iminoesters

The Pd-catalyzed cross-coupling ethoxycarbonylation of aryl boronic acids with N-aryl-α-iminoesters affords aryl carboxylic esters via carbonyl-imino σ bond cleavage. This unprecedented mode of reaction allows regioselective installation of the ethoxycarbonyl group into target molecules. Mechanism studies have revealed that an unusual 1,2-aryl shift process is involved in the transformation. The Royal Society of Chemistry.

Synthesis of α-alkenyl-α-amino esters via addition of potassium Alkenyltrifluoroborate salts to imine in the presence of Yb(OTf)3

A simple protocol which led to an effective construction of α-alkenyl-α-amino esters was achieved under mild conditions. This transformation proceeded by Yb-catalyzed addition of alkenyltrifluoroborates across the imine double bond. A variety of functional groups could be applicable to both partners.

Ruthenium(II)-catalyzed regioselective reductive coupling of α-imino esters with dienes

A method for the highly regioselective reductive coupling reaction of N-aryl-α-imino esters with dienes is described. The method utilizes the RuHCl(CO)(PPh3)3/iPrOH catalytic system under an Ar atmosphere and provides α-branched allylic α-amino acid derivatives. Application of this transformation to the concise synthesis of a natural plant growth regulator is demonstrated.

Palladium(II)-catalyzed enantioselective arylation of α-imino esters

A protocol for Pd(II)-catalyzed asymmetric arylation of N-aryl imino esters has been developed. The method affords a practical and direct access to chiral arylglycine derivatives in good yields and with high enantioselectivities.

Cu(II)-catalyzed intermolecular amidation of C-acylimine: A convenient access to gem-diamino acid derivatives

C-Acylimines 1 undergo intermolecular amidation with amides 2 to produce monoacyl gem-diamino acid derivatives 3 upon treatment with Cu(OTf)2 (20 mol %)/ PPh3 (20 mol %) under mild conditions. This method provides an efficient access to gem-diamino acid equivalents with good to excellent yields.

Synthesis and Cycloaddition Reactions of Ethyl Glyoxylate Imines. Synthesis of Substituted Furoquinolines and 7H-Indenoquinolines

Lewis acid catalyzed cycloaddition reactions of ethylglyoxylate imines to dihydrofuran and indene yield substituted hexahydrofuro- and tetrahydro-7H-indenoquinolines respectively.Oxidation of the adducts with 2,3-dichloro-5,6-dicyanobenzoquinone affords the corresponding aromatic compounds.