Cyclohexane and benzene amination by catalytic nitrene insertion into C-H bonds with the copper-homoscorpionate catalyst TpBr3Cu(NCMe)

Journal of the American Chemical Society

Volumn 125, Issue 40, 2003, Pages 12078-12079

  Díaz Requejo, M Mar ^a   Belderraín, Tomás R ^a   Nicasio, M Carmen ^a   Trofimenko, Swiatoslaw ^b   Pérez, Pedro J ^a  

^a UNIVERSITY OF HUELVA   (Spain)

^b UNIVERSITY OF DELAWARE   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

2 CYCLOHEXENONE; 4 TOLYLSULFONYL DERIVATIVE; BENZENE; BROMINE; CARBON; COPPER DERIVATIVE; CYCLOHEXANE; CYCLOHEXYLAMINE DERIVATIVE; HOMOSCORPIONATE; NITROGEN; SULFUR DERIVATIVE; UNCLASSIFIED DRUG;

AMINATION; ARTICLE; CATALYSIS; CHEMICAL BINDING; CHEMICAL STRUCTURE; COMPLEX FORMATION; LIGAND BINDING; PRODUCT RECOVERY; REACTION ANALYSIS; STRUCTURE ANALYSIS;

EID: 0141992731     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja037072l     Document Type: Article

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40. General catalytic procedure: inside a drybox, 0.025 mmol of 1 was dissolved in neat toluene or mesitylene (10 mL). Molecular sieves were added to diminish the presence of water. PhINTs (0.5 mmol) were added in one portion to the solution. After 1 h stirring, no solid PhINTs was observed. The greenish solution was filtered to retire the sieves and was investigated by GC. Volatiles were removed under vacuum, and the residue was investigated by NMR. Spectroscopic data were similar to those reported by Che for related compounds (ref 3h). In the case of the less reactive cyclohexane and benzene, a 1:20 ratio of 1 and PhINTs was employed, and the reaction times were up to 12-18 h. The cyclohexane derivative was identified by NMR, the spectra being identical to those reported by Che (ref 3h). The benzene derivative was characterized by comparison with an authentic sample prepared by reaction of aniline and tosyl chloride in the presence of base.