《Cleavage of ether, ester, and tosylate C(sp3)-O bonds by an iridium complex, initiated by oxidative addition of C-H bonds. Experimental and computational studies》 was written by Kundu, Sabuj; Choi, Jongwook; Wang, David Y.; Choliy, Yuriy; Emge, Thomas J.; Krogh-Jespersen, Karsten; Goldman, Alan S.. Application of 203245-16-3 And the article was included in Journal of the American Chemical Society on April 3 ,2013. The article conveys some information:
A pincer-ligated iridium complex, [(PCP)Ir] (1, PCP = κ3-C6H3-2,6-[CH2P(tBu)2]2), is found to undergo oxidative addition of C(sp3)-O bonds of Me esters (MeO2CR’), Me tosylate (MeOTs), and certain electron-poor Me aryl ethers (MeOAr). DFT calculations and mechanistic studies indicate that the reactions proceed via oxidative addition of C-H bonds followed by oxygenate migration, rather than by direct C-O addition Thus, Me aryl ethers react via addition of the methoxy C-H bond, followed by α-aryloxide migration to give cis-[(PCP)Ir(H)(CH2)(OAr)], followed by iridium-to-methylidene hydride migration to give [(PCP)Ir(Me)(OAr)]. Me acetate undergoes C-H bond addition at the carbomethoxy group to give [(PCP)Ir(H)[κ2-CH2OC(O)Me]] which then affords [(PCP-CH2)Ir(H)(κ2-O2CMe)] (6-Me) in which the methoxy C-O bond has been cleaved, and the methylene derived from the methoxy group has migrated into the PCP Cipso-Ir bond. Thermolysis of 6-Me ultimately gives [(PCP)Ir(CH3)(κ2-O2CR)], the net product of methoxy group C-O oxidative addition Reaction of [(PCP)Ir] with species of the type ROAr, RO2CMe or ROTs, where R possesses β-C-H bonds (e.g., R = Et or isopropyl), results in formation of [(PCP)Ir(H)(OAr)], [(PCP)Ir(H)(O2CMe)], or [(PCP)Ir(H)(OTs)], resp., along with the corresponding olefin or [(PCP)Ir(olefin)] complex. Like the C-O bond oxidative additions, these reactions also proceed via initial activation of a C-H bond; in this case, C-H addition at the β-position is followed by β-migration of the aryloxide, carboxylate, or tosylate group. Calculations indicate that the β-migration of the carboxylate group proceeds via an unusual six-membered cyclic transition state in which the alkoxy C-O bond is cleaved with no direct participation by the iridium center. In the experiment, the researchers used 1,2,3-Trifluoro-4-methoxybenzene(cas: 203245-16-3Application of 203245-16-3)
1,2,3-Trifluoro-4-methoxybenzene(cas: 203245-16-3) is a member of aromaticfluorinated building blocks. Depending on which substituents are present, fluoroaromatic intermediates can be converted into fluorinated or fluorine-free commercial end products.Fluorine-containing aromatics have been incorporated into drugs (hypnotics, tranquilizers, antiinflammatory agents, analgesics, antibacterials).Application of 203245-16-3
Referemce:
Ether – Wikipedia,
Ether | (C2H5)2O – PubChem