Palladium-Catalyzed Stereo- and Regiospecific Allylation of Aryl Halides with Homoallyl Alcohols via Retro-Allylation:  Selective Generation and Use of σ-Allylpalladium

Hayashi, Sayuri; Hirano, Koji; Yorimitsu, Hideki; Oshima, Koichiro

doi:10.1021/ja058055u

Cited by 110 publications

(27 citation statements)

References 10 publications

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“…This class of substrates, in particular in the context of aryl halide allylation, has predominantly been explored by the group of Oshima, in several papers starting from 2006 (Scheme ) 14a–14i…”

Section: Retro‐allylationmentioning

confidence: 99%

Transition‐Metal‐Mediated Cleavage and Activation of C–C Single Bonds

2012

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The activation and cleavage of C–C single bonds mediated by transition metal complexes is one of the most challenging reactions, both practically and in terms of understanding, in the field of metal organic chemistry. In this review the fundamental reactions – oxidative addition, β‐carbon elimination, retro‐allylation, and radical cleavage – so far successfully applied for this transformation are discussed in terms of their mechanisms, their intrinsic problems, and their published examples, which are still fairly rare. Decarbonylation, as another fundamental reaction, is only touched briefly. This group of reactions is today poised to set aside its shadow existence as an exotic reaction class. Meanwhile the number of catalytic and even enantioselective processes involvingC–C single bond cleavage is slowly increasing, although the substrates used in these reactions are still limited to quite special connection patterns. The basic challenges for the future and the paradigms concerning this reaction are presented.

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Section: Retro‐allylationmentioning

confidence: 99%

Transition‐Metal‐Mediated Cleavage and Activation of C–C Single Bonds

2012

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“…The reaction of this type was first developed by Kondo et al and several ruthenium-phosphine complexes were found to be effective [40]. Afterwards, Oshima and coworkers reported rhodium complex-catalyzed reactions [41]. For both of the catalysts, however, phosphorous additives, inorganic bases, an excess amount of allylic alcohols, and/or pressurized carbon monoxide are required.…”

Section: Ru/ceo -Catalyzed Organic Transformations Via Stable C-h or mentioning

confidence: 99%

Development of Ceria-Supported Ruthenium Catalysts Effective for Various Synthetic Reactions

2010

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Our recent results on organic transformations such as C-C bond formation via the activation of stable C-C or C-H bonds and aerobic oxidation of alcohols catalyzed by CeO 2 -supported ruthenium are reviewed. A simple, recyclable heterogeneous Ru/CeO 2 catalyst showed excellent activity for sequential transfer-allylation/ isomerization of homoallyl alcohols with aldehydes to saturated ketones via the C-C bond activation. While homogeneous ruthenium and rhodium complex catalysts require additives and/or pressurized CO, the reaction with Ru/CeO 2 smoothly proceeded in the absence of any additives. The Ru/CeO 2 catalyst also showed excellent activity for the addition of sp 2 C-H bonds of aromatic ketones to vinylsilanes. The Ru/CeO 2 catalyst realized the chelationassisted arylation of stable aromatic C-H bonds with aryl chlorides. The activity of the catalyst was greatly improved by the PPh 3 -modification under hydrogen atmosphere prior to the reactions. The catalyst acts heterogeneously without a significant leaching of ruthenium species, indicating that the Ru/CeO 2 catalyst has an advantage over homogeneous catalysts from practical and environmental points of view. The effects of chemical and physical properties of CeO 2 on the activity of CeO 2 -supported noble metal catalysts were examined. Porous CeO 2 powders were prepared by the coagulation of solvothermally synthesized colloidal ceria nanoparticles, and the thus-prepared CeO 2 powders showed an oxygen migration ability far superior to the CeO 2 samples prepared by the usual precipitation method. The ruthenium catalysts supported on the former CeO 2 powders showed a high activity for the aerobic oxidation of benzyl alcohol. The effects of the pore structure of CeO 2 powders on the activity of the Ru/CeO 2 catalysts are also discussed.

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“…In conclusion, we have demonstrated that a small amount of CuI‐phenanthroline complex catalyzes the CF 3 ‐group transfer cross‐coupling reactions of aryl/heteroaryl iodides25,26 with O ‐silylated hemiaminal 2 to give trifluoromethylated arenes in moderate to high yields. The substrate scope of the present methodology is broad and a variety of functional groups are tolerated.…”

Section: Methodsmentioning

confidence: 81%