56865-72-6Relevant academic research and scientific papers
Copper-catalyzed allylic amination of olefins with nitrosoarenes
Srivastava, Radhey S.
, p. 3271 - 3274 (2003)
The transition metal catalyzed allylic amination of olefins are studied. A screening of catalysts known for the intermediacy of PhNO in the amination of alkene with phenylhydroxylamine reveals that the hydrated copper salt in conjugation with copper powde
Palladium catalysed 3-component cascade synthesis of bis(2-arylallyl) tertiary amines from aryl iodides, allene and primary amines
Gai,Grigg,Collard,Muir
, p. 1712 - 1713 (2001)
A 3-component cascade synthesis of bis(2-arylallyl) tertiary amines from aryl iodide, allene and primary aliphatic amines is described; chiral amines give analogous products with no detectable racemisation; mixtures of two different aryl iodides can be ut
Iron-catalyzed allylic amination by nitroorganics
Srivastava, Radhey S.,Nicholas, Kenneth M.
, p. 2705 - 2706 (1998)
[CpFe(CO)2]2 catalyzes the reaction of nitroaromatics with olefins under CO to produce allyl amines regioselectively; a coordinated organonitrogen species is implicated as the active aminating agent.
Nickel-Catalyzed Mizoroki-Heck/Amination Cascade Reactions of o-Dihaloarenes with Allylamines: Synthesis of Indoles
Chen, Xu,Lin, Jin,Wang, Biao,Tian, Xu
supporting information, p. 7704 - 7708 (2020/10/12)
An efficient Mizoroki-Heck/amination cascade reaction of o-dihaloarenes with allylamines has been developed using nickel and IPr carbene ligand as catalyst. This protocol enables the synthesis of a broad range of substituted indoles by a cascade process, from readily available starting materials. Mechanistic studies suggest that the Mizoroki-Heck reaction occurred first under IPr-nickel catalysis.
Palladium-catalyzed oxidative arylacetoxylation of alkenes: Synthesis of indole and indoline derivatives
Karnakanti, Shuklachary,Zang, Zhong-Lin,Zhao, Sheng,Shao, Pan-Lin,Hu, Ping,He, Yun
supporting information, p. 11205 - 11208 (2017/10/17)
A method for the oxidative arylacetoxylation of alkenes has been developed to synthesize indole and indoline derivatives from readily accessible substrates. The cinnamyl tethered anilines with picolinamide as a directing group provided 3-substituted indoles via intramolecular oxidative arylacetoxylation, and the 2-methyl substituted cinnamyl anilines furnished indoline derivatives with 3-position quaternary stereocenters in good to excellent yields via sequential intramolecular oxidative arylacetoxylation, hydrolysis and oxidation steps.
A General Route to β-Substituted Pyrroles by Transition-Metal Catalysis
Bunrit, Anon,Sawadjoon, Supaporn,T?upova, Svetlana,Sj?berg, Per J. R.,Samec, Joseph S. M.
, p. 1450 - 1460 (2016/03/01)
An atom-efficient route to pyrroles substituted in the β-position has been achieved in four high yielding steps by a combination of Pd, Ru, and Fe catalysis with only water and ethene as side-products. The reaction is general and gives pyrroles substitute
Palladium- and nickel-catalyzed cross-couplings of unsaturated halides bearing relatively acidic protons with organozinc reagents
Manolikakes, Georg,Munoz Hernandez, Carmen,Schade, Matthias A.,Metzger, Albrecht,Knochel, Paul
supporting information; experimental part, p. 8422 - 8436 (2009/04/11)
(Chemical Equation Presented) A wide range of polyfunctional aryl, heteroaryl, alkyl, and benzylic zinc reagents were coupled with unsaturated aryl halides bearing an acidic NH or OH proton, using Pd(OAc)2 (1 mol %) and S-Phos (2 mol %) as catalyst without the need of protecting groups. A similar nickel-catalyzed reaction is described. The relative kinetic basicity of organozinc compounds as well as their stability toward acidic protons is also described.
Mechanistic studies of copper(I)-catalyzed allylic amination
Srivastava, Radhey S.,Tarver, Nathan R.,Nicholas, Kenneth M.
, p. 15250 - 15258 (2008/09/18)
The reactions of nitrosobenzene and N,N′-diethyl-4-nitrosoaniline with [Cu(CH3CN)4]PF6 provide novel Cu(I) complexes, [Cu(PhNO)3]PF6 (1) and [Cu(Et 2NPhNO)3]PF6 (2); in 2 the copper atom is N-coordinated to the nitrosoarenes in a distorted trigonal planar geometry. Complex 1 is strongly implicated as a reactive intermediate in the Cu(I)-catalyzed allylic amination of olefins based on (i) its isolation from the catalytic reaction, (ii) its stoichiometric regioselective allylic amination of α-methyl styrene (AMS), (iii) the non-involvement of free PhNO in its amination of AMS, and (iv) its function as a catalyst for the amination of alkenes from phenylhydroxylamine. The reaction between AMS and 1 (80°C, dioxane) is first order in both alkene and 1. Relative rate studies of the reaction of 1 with para substituted AMS derivatives gives a Hammett ρ value of -0.035. Alkene adducts isolated from the reaction of 1 with styrene and α-methylstyrene are formulated as [(PhNO)3Cu(η2- alkene)]PF6 (7,8) on the basis of spectroscopic characterization and thermolysis. PM3 and DFT MO calculations support the role of [(alkene)Cu(RNO)3]+ and (η1- or η3-allyl)Cu(RNO)2(RNHOH)+ complexes as probable catalytic intermediates and address the origin of the distinctive reaction regioselectivity. A mechanistic scheme is proposed which is consistent with the accumulated experimental and computational results.
Synthesis of secondary amines by titanium-mediated transfer of alkenyl groups from alcohols
Ramanathan, Balasubramanian,Odom, Aaron L.
, p. 9344 - 9345 (2007/10/03)
Reaction of Ti(NMe2)4 with allyl alcohols and primary amines leads to the selective formation of secondary allylic amines. The allyl transfer from the alcohol to the amine occurs with selective allylic transposition. Due to substituent effects in the reactions, we postulate that the reaction occurs through a [2 + 2]/retro-[2 + 2]-cycloaddition mechanism. It was also found that a similar reaction could be accomplished with homoallylic alcohol. In this case, the more complex mechanism leads to the formation of 1-aza-spiro[5.5]undecane. Possible pathways for the homoallylic transfer and cyclization are discussed. Copyright
Nitrosoarene-Cu(I) complexes are intermediates in copper-catalyzed allylic amination
Srivastava, Radhey S.,Khan, Masood A.,Nicholas, Kenneth M.
, p. 7278 - 7279 (2007/10/03)
Reactions of nitrosobenzene and N,N′-diethyl-4-nitrosoaniline with [Cu(CH3CN)4]PF6 produce novel homoleptic Cu(I)-nitrosoarene complexes, [Cu(ArNO)3]PF6, 1 (Ar = Ph) and 2 (Ar = 4-Et2NC6H4NO). The X-ray structure of 2 reveals that the copper is coordinated in a severely distorted trigonal planar geometry to the N-atom of the nitrosoarene ligand. Reactions of the PhNO complex 1 with olefins and an olefin/diene mixture provide evidence for its role as an intermediate and possibly the active nitrogen transfer agent in the Cu-catalyzed allylic amination of olefins by aryl hydroxylamines. Copyright
