Catalytic amination reactions mediated by Co(II) Schiff base complexes

Caselli, Alessandro; Gallo, Emma; Ragaini, Fabio; Oppezzo, A.; Cenini, Sergio

doi:10.1016/j.jorganchem.2005.01.021

Cited by 26 publications

(9 citation statements)

References 78 publications

(83 reference statements)

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“…For related structures, see, for example: Adrian et al (2008). For background to applications of palladium(II) complexes, see, for example: Abu-Surrah et al (1999); Adrian et al (2008); Ayala et al (2004); Caselli et al (2005); Lai et al (2005); Pou et al (2007); Ramírez et al (2008); Roy et al (2008). For bondlength data, see: Allen et al (1987).…”

Section: Related Literaturementioning

confidence: 99%

{2,2′-[(2,2-Dimethylpropane-1,3-diyl)bis(nitrilomethylidyne)]diphenolato}palladium(II) ethanol hemisolvate

et al. 2008

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The asymmetric unit of the title complex, [Pd(C19H20N2O2)]·0.5C2H5OH, contains two molecules of a PdII complex of a Schiff base ligand with an N2O2 donor set and one ethanol molecule. The PdII centers are in distorted square-planar geometries with the N2O2 donor atoms of the tetradentate Schiff base dianions. The ethanol molecule takes part in an O—H⋯O hydrogen bond. In the crystal structure, molecules are stacked approximately along the b-axis direction. The O atom and three H atoms of the solvent molecule are disordered over two positions; the site occupancy factors are ca 0.8 and 0.2.

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Section: Related Literaturementioning

confidence: 99%

{2,2′-[(2,2-Dimethylpropane-1,3-diyl)bis(nitrilomethylidyne)]diphenolato}palladium(II) ethanol hemisolvate

et al. 2008

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“…In our ongoing study on amination reactions catalyzed by transition metals,13,14 we recently reported the use of aromatic azides in the amination of unsaturated hydrocarbons catalyzed by ruthenium14–16 and cobalt17,18 porphyrin complexes. The metal coordination mode of the porphyrin complexes renders them a unique class of catalysts for N‐group transfer reactions,19 and indeed, the first transition‐metal complexes that showed good activity as catalysts in aziridination reactions were metalloporphyrins 20.…”

Section: Introductionmentioning

confidence: 99%

Allylic Amination and Aziridination of Olefins by Aryl Azides Catalyzed by Co^II(tpp): A Synthetic and Mechanistic Study

et al. 2008

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CoII (tpp) catalyzes the reaction of aromatic azides (ArN 3 ) with nonactivated olefins to yield allylic amines or aziridines in moderate-to-good yields. The chemoselectivity of the catalytic reaction is particularly high. Depending on the substrate employed, allylic amines or aziridines can be obtained. The reaction mechanism was investigated, and the reaction proceeds through reversible coordination of the aryl azide to the Co II -porphyrin complex. The often postulated "nitrene" complex is not an intermediate in this reaction. The kinetics for the allylic amination is first order in azide, Co(tpp), and olefin. For the aziridination, the kinetics is again first order

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“…However, the generation of a stoichiometric amount of iodobenzene is still a major drawback associated with the use of hypervalent iodine reagents. Amination reactions have been developed by using various metal complexes, such as Co,7b,c Ru,7a Cu,8, 9f,l,s Au,9p Ag,9i,q and Pd9m to catalyze nitrene insertion, but rhodium dimers remain the most employed complexes 9a–c,g,h,j,k,n,o,r,t. With all these methods in hand, intramolecular CH insertion is now an established reaction that is used in total synthesis to form β‐ or γ‐amino alcohols 11.…”

Section: Introductionmentioning

confidence: 99%

N‐Tosyloxycarbamates as Reagents in Rhodium‐Catalyzed CH Amination Reactions

Huard

Lebel

2008

Chemistry A European J

173

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Metal nitrenes for use in C-H insertion reactions were obtained from N-tosyloxycarbamates in the presence of an inorganic base and a rhodium(II) dimer complex catalyst. The C-H amination reaction proceeds smoothly, and the potassium tosylate that forms as a byproduct is easily removed by filtration or an aqueous workup. This new methodology allows the amination of ethereal, benzylic, tertiary, secondary, and even primary C-H bonds. The intramolecular reaction provides an interesting route to various substituted oxazolidinones, whereas the intermolecular reaction gives trichloroethoxycarbonyl-protected amines that can be isolated with moderate to excellent yields and that cleave easily to produce the corresponding free amine. The development, scope, and limitations of the reactions are discussed herein. Isotopic effects and the electronic nature of the transition state are used to discuss the mechanism of the reaction.

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Catalytic amination reactions mediated by Co(II) Schiff base complexes

Cited by 26 publications

References 78 publications

{2,2′-[(2,2-Dimethylpropane-1,3-diyl)bis(nitrilomethylidyne)]diphenolato}palladium(II) ethanol hemisolvate

{2,2′-[(2,2-Dimethylpropane-1,3-diyl)bis(nitrilomethylidyne)]diphenolato}palladium(II) ethanol hemisolvate

Allylic Amination and Aziridination of Olefins by Aryl Azides Catalyzed by Co^II(tpp): A Synthetic and Mechanistic Study

N‐Tosyloxycarbamates as Reagents in Rhodium‐Catalyzed CH Amination Reactions

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Catalytic amination reactions mediated by Co(II) Schiff base complexes

Cited by 26 publications

References 78 publications

{2,2′-[(2,2-Dimethylpropane-1,3-diyl)bis(nitrilomethylidyne)]diphenolato}palladium(II) ethanol hemisolvate

{2,2′-[(2,2-Dimethylpropane-1,3-diyl)bis(nitrilomethylidyne)]diphenolato}palladium(II) ethanol hemisolvate

Allylic Amination and Aziridination of Olefins by Aryl Azides Catalyzed by CoII(tpp): A Synthetic and Mechanistic Study

N‐Tosyloxycarbamates as Reagents in Rhodium‐Catalyzed CH Amination Reactions

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Allylic Amination and Aziridination of Olefins by Aryl Azides Catalyzed by Co^II(tpp): A Synthetic and Mechanistic Study