14064-75-6Relevant academic research and scientific papers
Bifunctional Iminophosphorane-Catalyzed Enantioselective Sulfa-Michael Addition to Unactivated α,β-Unsaturated Amides
Dixon, Darren J.,Formica, Michele,Hamlin, Trevor A.,Rozsar, Daniel,Yamazaki, Ken
supporting information, p. 1006 - 1015 (2022/02/03)
The first metal-free catalytic intermolecular enantioselective Michael addition to unactivated α,β-unsaturated amides is described. Consistently high enantiomeric excesses and yields were obtained over a wide range of alkyl thiol pronucleophiles and elect
Copper(I)-Catalyzed Asymmetric 1,4-Conjugate Hydrophosphination of α,β-Unsaturated Amides
Li, Yan-Bo,Tian, Hu,Yin, Liang
supporting information, p. 20098 - 20106 (2021/01/01)
A catalytic asymmetric conjugate hydrophosphination of α,β-unsaturated amides is accomplished by virtue of the strong nucleophilicity of copper(I)-PPh2 species, which provides an array of chiral phosphines bearing an amide moiety in high to excellent yields with excellent enantioselectivity. Furthermore, the dynamic kinetic resolution of unsymmetrical diarylphosphines (HPAr1Ar2) is successfully carried out through the copper(I)-catalyzed conjugate addition to α,β-unsaturated amides, which affords P-chiral phosphines with good-to-high diastereoselectivity and high enantioselectivity. 1H NMR studies show that the precoordination of HPPh2 to copper(I)-bisphosphine complex is critical for the efficient deprotonation by Barton's Base. Moreover, the relative stability of the copper(I)-(R,RP)-TANIAPHOS complex in the presence of excessive HPPh2, confirmed by 31P NMR studies, is pivotal for the high asymmetric induction, as the ligand exchange between bisphosphine and HPPh2 would significantly reduce the enantioselectivity. At last, a double catalytic asymmetric conjugate hydrophosphination furnishes the corresponding product in high yield with high diastereoselectivity and excellent enantioselectivity, which is transformed to a chiral pincer palladium complex in moderate yield. This chiral palladium complex is demonstrated as an excellent catalyst in the asymmetric conjugate hydrophosphination of chalcone.
α,β-Unsaturated Amides as Dipolarophiles: Catalytic Asymmetric exo-Selective 1,3-Dipolar Cycloaddition with Nitrones
Zhang, Ming,Kumagai, Naoya,Shibasaki, Masakatsu
supporting information, p. 12450 - 12455 (2017/09/18)
1,3-Dipolar cycloaddition is a commonly exploited method to access 5-membered chemical entities with a variety of peripheral functionalities and their stereochemical arrangements. Nitrones are isolable 1,3-dipoles that exhibit sufficient reactivity toward electron-deficient olefins in the presence of Lewis acids to deliver highly substituted isoxazolidines. Herein we document that α,β-unsaturated amides, generally regarded as barely reactive in a 1,3-dipolar reaction manifold, were effectively activated using the designed 7-azaindoline auxiliary in an In(OTf)3/bishydroxamic acid catalytic system. The broad substrate scope and clean removal of the 7-azaindoline auxiliary from the product highlight the synthetic utility of the present catalysis.
Lewis Acid Enabled Copper-Catalyzed Asymmetric Synthesis of Chiral β-Substituted Amides
Rodríguez-Fernández, Mamen,Yan, Xingchen,Collados, Juan F.,White, Paul B.,Harutyunyan, Syuzanna R.
supporting information, p. 14224 - 14231 (2017/10/17)
Here we report that readily available silyl- and boron-based Lewis acids in combination with chiral copper catalysts are able to overcome the reactivity issues of unactivated enamides, known as the least reactive carboxylic acid derivatives, toward alkyla
Mechanistic insights into polar monomer insertion polymerization from acrylamides
Friedberger, Tobias,Wucher, Philipp,Mecking, Stefan
scheme or table, p. 1010 - 1018 (2012/03/12)
Figure Persented: N-Isopropyl acrylamide (NIPAM), N,N-dimethyl acrylamide (DMAA), and 2-acetamidoethyl acrylate (AcAMEA) were copolymerized with ethylene employing [(P∧O)PdMe(DMSO)] (1-DMSO; P∧O = κ2-P,O- Ar2PC6H4SO2O with Ar = 2-MeOC 6H4) as a catalyst precursor. Inhibition studies with nonpolymerizable polar additives show that reversible κ-O-coordination of free amide retards polymerization significantly. Retardation of polymerization increases in the order ethyl acetate ? methyl ethyl sulfone 6H11NO 2)nMe] (n ≤ 3), as determined by electrospray ionization mass spectrometry. The solid-state structure of the methanol adduct of the 2,1-insertion product of NIPAM into 1-DMSO, [(P∧O) Pd{η1-CH(CONHiPr)CH2CH3} (κ1-O-MeOD)] (2-MeOD), was determined by single crystal X-ray diffraction. Both 2,1- and 1,2-insertions of DMAA into the Pd-Me bond of a [(P∧O)PdMe] fragment occur to afford a ca. 4:1 mixture of chelates [(P∧O)Pd{κ2-C,O-C(CH2CH3)C(O)NMe 2}] (3) and [(P∧O)Pd{κ2-C,O-CH 2C(CH3)C(O)NMe2}] (4). The four-membered chelate of 3 is opened by coordination of 2,6-lutidine (3 + 2,6-lutidine ? 3-LUT) with ΔH° = -41.8(10.5) kJ and ΔS° = -115(37) J mol-1 K-1.
Stereoselective 1,4-addition of Grignard reagents to α,β-enamides using a combined chiral auxiliary-catalyst approach
Biswas, Kallolmay,Woodward, Simon
, p. 1702 - 1708 (2008/12/21)
A catalyst composed of (R,R)-MeDuphos and CuBr·SMe2 catalyzes the addition of RMgBr (R = Et, C5H11, Ph) to simple enamides (E)-Me2NCOCH{double bond, long}CHR1 (R1 = Me, C5H1
METHOD FOR PRODUCTION OF Γ(A),Γ(B)-UNSATURATED AMIDE COMPOUNDS
-
Page/Page column 12; 13, (2010/02/10)
The invention relates to a method for production of α,β-unsaturated amide compounds of general formula (I): whereby (A) a protective group is introduced into a molecule of general formula (II) to give a compound of formula (III), (B) the compound obtained is reacted in the presence of (i) a dehydrogenation catalyst and (ii) a suitable oxidation agent and (C) the protective groups are removed.
Palladium-catalyzed conversion of benzylic and allylic halides into α-aryl and β,γ-unsaturated tertiary amides by the use of a carbamoylsilane
Cunico, Robert F.,Pandey, Rajesh K.
, p. 9048 - 9050 (2007/10/03)
Treatment of allylic and benzylic halides with N,N- dimethylcarbamoyl(trimethyl)silane in the presence of tetrakis- (triphenylphosphine)palladium(0) affords tertiary amides, which arise from the replacement of the halogen by the N,N-dimethylcarbamoyl group.
The extraordinary reactions of phenyldimethylsilyllithium with N,N-disubstituted amides
Buswell, Marina,Fleming, Ian,Ghosh, Usha,Mack, Stephen,Russell, Matthew,Clark, Barry P.
, p. 3006 - 3017 (2007/10/03)
The reactions of the silyllithium reagent with tertiary amides was discussed. The enediamines were easily isomerized from cis to trans, easily oxidized to dienediamines and were hydrolyzed to α-aminoketones. If the two equivalents of the silyllithium reagent were used, the product was an α-silylamine. The results show that each member of the homologous series of amides gives rise to a substantially different product.
Asymmetric synthesis of anti-α-alkyl-β-amino carboxamides
Davies, Stephen G.,Edwards, Alison J.,Walters, Iain A. S.
, p. 175 - 183 (2007/10/02)
The alkylation reactions of enolates derived from the highly diastereoselective conjugate additions of lithium (R)-N-benzyl-N-α-methylbenzylamide (R)-1 to N,N-dimethyl crotonamide 2 and N,N-dimethyl cinnamide 3 have been investigated.The alkylations of en
