141264-25-7Relevant articles and documents
Oxidation of the methyl groups of N,N-dimethylbenzamides by a cytochrome P450 monooxygenase model system
Iley, Jim
, p. 4921 - 4922 (1990)
Oxidation of N,N-dimethylbenzamides to the corresponding N,N-formyl-N-methylbenzamides using tetraphenylporphyrinato-iron(III)-ButOOH is independent of the substituent in the aryl ring of the benzamide group and subject to a kinetic deuterium isotope effect of 5.6. These results are consistent with a mechanism involving direct hydrogen atom abstraction from the substrate.
Copper-Catalyzed Asymmetric Protoboration of β-Amidoacrylonitriles and β-Amidoacrylate Esters: An Efficient Approach to Functionalized Chiral α-Amino Boronate Esters
Chen, Lili,Zou, Xiaoliang,Zhao, Haonan,Xu, Senmiao
supporting information, p. 3676 - 3679 (2017/07/15)
A copper-catalyzed asymmetric protoboration of both Z-β-amidoacrylonitriles and ethyl E-β-amidoacrylates using bis(pinacolato)diboron has been developed for the first time. The process tolerates a vast array of substrates, delivering a series of stable functionalized chiral α-amino boronate esters in good yields and enantioselectivities under mild reaction conditions. The current method is also applicable for gram-scale synthesis without erosion of enantioselectivity. This work provides an attractive and complementary approach to synthesizing enantioriched chiral α-amino boronate esters.
STEREOSELECTIVE SYNTHESIS OF HIGHLY SUBSTITUTED ENAMIDES
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Page/Page column 33, (2013/02/28)
The disclosure provides new methods for the oxidative Heck cross-coupling reaction with electron-rich alkenes such as substituted β-amidoacrylate and other related substituted enamides. Previously, functionalization of enamides under Heck conditions has b
Oxidation of tertiary benzamides by 5,10,15,20-tetraphenyl- porphyrinatoironIII chloride-tert-butylhydroperoxide
Constantino, Luis,Iley, Jim
, p. 1894 - 1900 (2007/10/03)
Tertiary benzamides are oxidized by the 5,10,15,20- tetraphenylporphyrinatoiron(III) chloride-ButOOH system at the α-position of the N-alkyl groups. The major products are N-acylamides, although small amounts of secondary amides, the products of dealkylation, are also formed. Plots of initial rate versus initial substrate concentration for these reactions are curved, suggesting formation of an oxidant-substrate complex. The reaction rates are almost insensitive to the substituent in the benzamide moiety, but there is a kinetic deuterium isotope effect of 5.6 for the reaction of the N,N-(CH3)2 and N,N-(CD3) 2 compounds. Comparison of the reaction products from N-alkyl-N-methylbenzamides reveals that, for all compounds studied except N-cyclopropyl-N-methylbenzamide, oxidation of the alkyl group is preferred, strongly so (by a factor of ca. 8) for N-allyl-N-methylbenzamide. In contrast to microsomal oxidation, there is no steric hindrance to oxidation of an isopropyl group. Thus, we propose that these reactions proceed via hydrogen atom abstraction to form an α-carbon-centred radical and we attribute the observed diminished reactivity of the N-cyclopropyl group to its known reluctance to form a cyclopropyl radical. Oxidation of N-methyl-N-(2,2,3,3- tetramethylcyclopropyl)methylbenzamide provides preliminary evidence for rearrangement of an intermediate radical. While it remains unclear how these reactions proceed directly to the N-acyl products, we have established that N-hydroxymethyl, N-alkoxymethyl and N-alkylperoxymethyl intermediates are not involved.
