84039-68-9

Upstream product

• 201230-82-2 carbon monoxide 
• 42599-24-6 E-styryl iodide 
• 109-89-7 diethylamine 
• 103-64-0 bromostyrene 
• 100-52-7 benzaldehyde 
• 173170-50-8 3-(Diethoxyphosphoryl)-N,N-diethyl-2-oxopropanamid 
• 1914-59-6 (E)-2-oxo-4-phenyl-3-butenoic acid 

Relevant academic research and scientific papers

Highly efficient synthesis of trans-β,γ-unsaturated α-keto amides

A highly efficient, metal-free, and selective access to trans-β,γ-unsaturated α-keto amides is described via peptidic coupling, involving easy to prepare trans-β,γ-unsaturated α-keto acids and commercially available amines. Georg Thieme Verlag Stuttgart.

Syntheses of 2,3-dioxoalkylphosphonates and other novel β-ketophosphonates as well as of a phosphinopyruvamide (= (alkyloxyphosphinyl)pyruvamide)

The new 3-(diethoxyphosphoryl)-2-oxopropanoates 5 and 6 and -propanamides 1-4 with various amino substituents at C(3) were prepared (Scheme 2). These compounds exist, depending on N-substitution, as pure (E)-enols (in the case of 1 and 5) or as a mixture of three tautomeric forms (in the case of 1-4 and 6). The configuration could be unambiguously assigned from the 1H-, 13C-, and 31P-NMR spectra. Phosphinopyruvamide ( = (alkyloxyphosphinyl)pyruvamide) 9 was prepared in a similar manner in spite of the instability of phosphinate-derived carbanions. Some 3-(ethoxyimino)-2-oxobutylphosphonates, 11-13 (Scheme 5), and various 3,3-dimethoxy-2-oxoalkylphosphonates, 19-23 and 26-33 (Scheme 6), were available from the reaction of lithioalkylphosphonates with 2-(ethoxyimino)propanoates and 2,2-dimethoxyalkanoates, respectively. The 3,3-dimethoxybutylphosphonates 20, and 26-30 were cleaved to give 2,3-dioxobutylphosphonates 34-39 (Scheme 6). This method provides easy access to a new class of potentially pharmaceutically useful compounds.

Palladium-Catalyzed Double-Carbonylation of Alkenyl Halides with Secondary Amines to Give α-Keto Amides

The double-carbonylation reaction of alkenyl halides with diethylamine in the presence of palladium catalysts has been examined in detail.The reaction gives α-keto amide together with amide, the single carbonylation by-product.The yield of α-keto amide is strongly dependent on the nature of alkenyl halide.Alkenyl bromides or iodides having phenyl group(s) as substituent(s) on the vinyl group are successfully double-carbonylated under appropriate reaction conditions and the corresponding α-keto amides are obtained in good to modest yields together with amides.In contrast, the reactions of alkenyl halides without a phenyl group give amides exclusively.In order to clarify the reason for the substrate-specificity in the reaction, series of alkenyl- and alkenoylpalladium(II) complexes, the presumed intermediates in the catalytic reactions, have been prepared and their reactions with secondary amines, carbon monoxide, and alkenyl halides were examined.The study suggests the operation of three types of processes for amide formation in the catalytic reactions.Possible mechanism for amide as well as α-keto amide formation are discussed.

CATALYTIC DOUBLE CARBONYLATION OF ORGANOHALOGEN COMPOUNDS PROMOTED BY PALLADIUM COMPLEXES

Various organohalogen compounds can be catalytically converted into α-keto amides on reaction with carbon monoxide and amines.Tertiary phosphine-coordinated palladium compounds are particularly suitable as the double carbonylation catalyst.