14064-75-6Relevant articles and documents
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
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.
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.