1565-75-9Relevant articles and documents
Reactions of Palladium(II) with Organic Compounds. Part 5. Effect of Reaction Conditions upon Products of Oxidation of α-Methylstyrene
Norman, Richard O. C.,Thomas, C. Barry,Watson, Grenville
, p. 1099 - 1104 (1980)
The effects upon product distribution of varying the temperature, time of reaction, and reagent concentrations have been investigated in the oxidation of α-methylstyrene by palladium(II) acetate.Two reaction pathways have been identified.A ?-allylic organopalladium compound decomposes slowly in a process catalysed by excess of the alkene to give 2-phenylprop-2-enyl acetate.The second reaction leads to competitive formation of enolic acetates and oxidative dimers but the organopalladium species involved has not been unambiguously identified.The addition of sodium acetate to the reaction, contrary to earlier reports, has only a marginal effect upon the distribution of products.
Comparative Studies on the Addition Reactions of the Normant Reagent ("CH3MgBr" + CuBr) and the New Tetrahydrofuran-Soluble Magnesium Methylcuprates MgmCun(CH3)2m+n with Phenylacetylene
Ashby, E. C.,Smith, R. Scott,Goel, A. B.
, p. 5133 - 5139 (1981)
Reactions of phenylacetylene with the Normant reagent ("CH3MgBr" + CuBr) and the THF-soluble magnesium methyl cuprates MgmCun(CH3)2m+n obtained from the reaction of (CH3)2Mg with CuBr have been studied in detail.An attempt to determine the reactive species in Normant reagents was made by studying the rate of reaction of the Normant reagent with phenylacetylene compared to the rate observed with various magnesium methylcuprates.Cu4Mg(CH3)6 and Cu6Mg(CH3)8 have been shown to be the most probable candidates responsible for reactions involving the Normant reagent with alkynes.The effect of MgBr2 and LiBr on the reactivity and the product selectivity has also been studied.
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Georgiou et al.
, p. 253 (1974)
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Kampmeier,Fantazier
, p. 1959 (1966)
Organophotoredox-Catalyzed Decarboxylative C(sp3)-O Bond Formation
Shibutani, Shotaro,Kodo, Taiga,Takeda, Mitsutaka,Nagao, Kazunori,Tokunaga, Norihito,Sasaki, Yusuke,Ohmiya, Hirohisa
, p. 1211 - 1216 (2020)
This manuscript reports a visible-light-mediated organosulfide catalysis that enables the decarboxylative coupling between simple aliphatic alcohol and tertiary or secondary alkyl carboxylic acid-derived redox active esters to produce a C(sp3)-O-C(sp3) fragment. Results of the coupling using other heteroatom nucleophiles such as water, amides, and thiols are also described.
Palladium-Aminopyridine Catalyzed C?H Oxygenation: Probing the Nature of Metal Based Oxidant
Lubov, Dmitry P.,Bryliakova, Anna A.,Samsonenko, Denis G.,Sheven, Dmitriy G.,Talsi, Evgenii P.,Bryliakov, Konstantin P.
, p. 5109 - 5120 (2021/11/10)
A mechanistic study of direct selective oxidation of benzylic C(sp3)?H groups with peracetic acid, catalyzed by palladium complexes with tripodal amino-tris(pyriylmethyl) ligands, is presented. The oxidation of arylalkanes having secondary and tertiary benzylic C?H groups, predominantly yields, depending on the substrate and conditions, either the corresponding ketones or alcohols. One of the three 2-pyriylmethyl moieties, which is pending in the starting catalyst, apparently, facilitates the active species formation and takes part in stabilization of the high-valent Pd center in the active species, occupying the axial coordination site of palladium. The catalytic, as well as isotopic labeling experiments, in combination with ESI-MS data and DFT calculations, point out palladium oxyl species as possible catalytically active sites, operating essentially via C?H abstraction/oxygen rebound pathway. For the ketones formation, O?H abstraction/в-scission mechanism has been proposed.
Combination of organocatalytic oxidation of alcohols and organolithium chemistry (RLi) in aqueous media, at room temperature and under aerobic conditions
Elorriaga, David,García-álvarez, Joaquín,González-Sabín, Javier,Hevia, Eva,Morís, Francisco,Presa Soto, Alejandro,Ríos-Lombardía, Nicolás,Rodríguez-álvarez, María Jesús
, p. 8932 - 8935 (2020/08/17)
A tandem protocol to access tertiary alcohols has been developed which combines the organocatalytic oxidation of secondary alcohols to ketones followed by their chemoselective addition by several RLi reagents. Reactions take place at room temperature, under air and in aqueous solutions, a trio of conditions that are typically forbidden in polar organometallic chemistry.
