94871-36-0Relevant academic research and scientific papers
Bidentate NHC-Cobalt Catalysts for the Hydrogenation of Hindered Alkenes
Wei, Zeyuan,Wang, Yujie,Li, Yibiao,Ferraccioli, Raffaella,Liu, Qiang
, p. 3082 - 3087 (2020/10/02)
Herein, we report a series of easily accessible bidentate N-heterocyclic carbene (NHC) cobalt catalysts, which enable the hydrogenation of hindered alkenes under mild conditions. The four-coordinated bidentate NHC-Co(II) complexes were characterized by X-ray diffraction, elemental analysis, ESI-HRMS, and magnetic moment measurements, revealing a distorted-tetrahedral geometry and a high-spin configuration of the metal center. The activity of the in situ formed catalytic system, which was obtained from easily available NHC precursors, CoCl2, and NaHBEt3, was identical with those of well-defined NHC-cobalt catalysts. This highlights the potential utility of this reaction system.
Substitution of Secondary Benzylic Phosphates with Diarylmethyl Anions
Shinohara, Riku,Kawashima, Hidehisa,Ogawa, Narihito,Kobayashi, Yuichi
, p. 2717 - 2725 (2019/04/04)
Substitution of diethyl and diphenyl benzylic phosphates, Alk-CH(Ar1)OP(O)(OR)2 (R = Et, Ph; Alk = Me, Et, i-Pr; Ar1 = aryl), with the anions derived from Ar2CH2 (Ph2CH2,9H-xanthene and fluorene) and n-BuLi at –15 °C was studied. For phosphates with Me as an Alk, diethyl phosphates produced Me-CH(Ar1)CH(Ar2)2 (Ar1 = 4-halo-, 4-CN, 4-Me-, 2-Me, 2-Br-, 3-MeO-phenyl and 2-naphthyl). However, an unwanted substitution at the Et group competed with phosphates of Alk = Et- and i-Pr. Fortunately, the corresponding diphenyl phosphates cleanly underwent the desired substitution. Two enantioenriched phosphates, MeCH(Ph)OP(O)(OEt)2 and EtCH(Ph)OP(O)(OPh)2, proceeded with complete inversion of the stereochemistry.
Friedel-Crafts alkylation of benzene with 1,2-diphenyl-2-propanol, 1-chloro-2,3-diphenylpropane and 2-methyl-1-phenyl-2-butanol
Khalaf, Ali A.,Awad, Ibrahim M.,El-Emary,El-Aal, H.A.K. Abd
experimental part, p. 595 - 600 (2011/08/21)
The alkylation of benzene with 1,2-diphenyl-2-propanol (1) using AlCl 3/CH3NO2 catalyst gave a mixture of 1,2,2- (4) and 1,1,2-triphenylpropane (5) as product alkylates. With 85% H 2SO4 catalyst, the product consisted of E-1,2-diphenylpropene (6) after 2 h of a mixture of 5 and 6 after 18 h. Similar alkylation of benzene with 1-chloro-2,3-diphenylpropane (2) using AlCl 3 catalyst gave a mixture consisting of 4, 5 and 6. Finally, alkylation of benzene with 2-methyl-1-phenyl-2-butanol (3) using AlCl 3/CH3NO2 gave 2-methyl-1,1-diphenylbutane (10) as sole product alkylate. The identities of the products were confirmed spectroscopically and by comparison with unequivocally prepared samples. Mechanisms are proposed to rationalise the observed results.
1-(N,N-diisopropylcarbamoyloxy)-1-tosyl-1-alkenes - a2d 1 synthons via tandem umpolung
Chen, Yue-Lei,Hoppe, Dieter
supporting information; experimental part, p. 4188 - 4194 (2009/09/25)
(Equation Presented) 1-(N,N-Diisopropylcarbamoyloxy)-1-tosyl-alkenes have been developed as an a2d1 synthon via tandem umpolung. Upon addition of Grignard reagents and further quench by carbonyl compounds, this synthon produces α,α′-
Radical ions in photochemistry. Carbon-carbon bond cleavage of radical cations in solution: Theory and application
Popielarz,Arnold
, p. 3068 - 3082 (2007/10/02)
The cleavage of radical cations of two series of alkanes, 1,1,2-triaryl- and 1,1,2,2-tetraarylalkanes, generated by photoinduced single electron transfer in acetonitrile-methanol, occurs with formation of radical and carbocation fragments. The radical cations of some unsymmetrically substituted alkanes cleave to give all four of the possible products, two hydrocarbons emanating from the radicals and two methyl ethers from the carbocations, in proportion to the oxidation potentials of the two possible radical fragments. There is an excellent linear correlation between the logarithm of the observed ratio of products and that calculated from the reported electrochemically determined oxidation potentials (r = 0.998, 5 points). The proportionality constant (1.27) for this relationship is close to unity which indicates that the product ratio is determined by the relative rates of cleavage in the two possible modes or by equilibration of the radicals and carbocations before separation of the geminate radical carbocation pair and not by equilibration upon reencounter of freely solvated radical and carbocation fragments. The effect of temperature on the relative oxidation potentials of the radicals studied is small and can be neglected when radicals of the same order (i.e., both secondary or both tertiary) and of similar size are compared. The ratio of products obtained upon cleavage of the radical cation at 25 °C can be used to determined standard oxidation potentials of radicals. The oxidation potential of the diphenylmethyl radical (0.350 V vs SCE) has been accepted as the primary standard and the (4-methyl-phenyl)phenylmethyl (0.265 V) and bis(4-methylphenyl)methyl (0.188 V) radicals are established as secondary standards against which the oxidation potentials of other radicals can be measured. Oxidation potentials of several 4-substituted cumyl radicals have been determined by this photochemical method. There is a good (r = 0.987, 5 points) linear correlation between the measured oxidation potentials and the σ+ substituent constants. The reaction constant is appropriately negative and large (p = -6).
