106731-06-0Relevant academic research and scientific papers
Palladium and Nickel Catalyzed Suzuki Cross-Coupling with Alkyl Fluorides
Balaraman, Kaluvu,Wolf, Christian
supporting information, p. 8994 - 8999 (2021/11/20)
Suzuki cross-coupling of benzylic and unactivated aliphatic fluorides with aryl- and alkenylboronic acids has been achieved via mechanistically distinct Pd and Ni catalyzed pathways that outperform competing protodeboronation, β-hydride elimination, and h
Vinyl sulfonamide or vinyl amide compound as well as preparation method and application thereof (by machine translation)
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Paragraph 0087-0091, (2020/12/14)
The structure is shown in the formula I, and the definition of each substituent is as described in the specification and the claims. The compounds of the invention are useful in the preparation of medicaments for the treatment of diseases or disorders mediated by TEAADs. (by machine translation)
Dual copper- and photoredox-catalysed C(sp2)-C(sp3) coupling
McLean, Euan B.,Gauchot, Vincent,Brunen, Sebastian,Burns, David J.,Lee, Ai-Lan
supporting information, p. 4238 - 4241 (2019/04/30)
The use of copper catalysis with visible light photoredox catalysis in a cooperative fashion has recently emerged as a versatile means of developing new C-C bond forming reactions. In this work, dual copper and photoredox catalysis is exploited to effect C(sp2)-C(sp3) cross-couplings between aryl boronic acids and benzyl bromides.
Superacid BF3-H2O promoted benzylation of arenes with benzyl alcohols and acetates initiated by trace water
Zhang, Shuting,Zhang, Xiaohui,Ling, Xuege,He, Chao,Huang, Ruofeng,Pan, Jing,Li, Jiaqiang,Xiong, Yan
, p. 30768 - 30774 (2014/08/05)
A convenient procedure employing simple starting materials benzyl alcohols and acetates as the benzyl donors to assemble a series of diarylalkanes through benzylation of arenes using in situ prepared superacid BF3-H 2O as an efficient promoter has been developed. The beneficial role of water in the reaction has been clarified with combination of control experiments and 11B NMR analysis. This reaction is a self-promoted model, which is triggered by the trace of water and continuously promoted by self released by-product water (or carboxylic acid). A wide range of substrates are investigated and the moderate to excellent yields and the good regioselectivities for secondary benzyl alcohols as well as arenes bearing electron-withdrawing groups have been achieved. As a result, moisture in the reaction system has been utilized as an efficient initiator in all benzylation cases.
A Study of N-Nitrosoamide-Mediated Friedel-Crafts Type Benzylation of Benzene-Toluene and Benzene-Anisole1a
Darbeau, Ron W.,White, Emil H.
, p. 1121 - 1131 (2007/10/03)
Nitrogen-separated carbocation-carboxylate ion pairs were employed as sources of carbocations in the alkylation of aromatic compounds. The N-nitrosoamide approach to these nitrogenous-molecule-separated ion pairs is an excellent alternative to the standard acid-catalyzed Friedel-Crafts approach for studies of the alkylation because of the following variables: high reactivity of the electrophile, stability of the products, strict kinetic control, homogeneity, lack of over alkylation, straightforward chemistry, and good product balance. In deaminative benzylations of benzene-toluene and anisole-benzene mixtures, the values of kX/kB and % meta isomer are significantly different from those observed in the standard benzylations in a manner that indicates the deaminative electrophiles are more reactive than those generated by the standard Friedel-Crafts approach. The reactions show a direct proportionality between inter- and intramolecular selectivities and thus follow the Brown selectivity relationship (BSR). The benzylation of 2,4,6-trideuteriotoluene provided no evidence for deuterium rearrangements (or coupled benzyl rearrangements) in the arenium ion intermediate. Kinetic isotope effects were not detected. The methyl substituent on toluene appears to affect intermolecular selectivity (kT/kB) and intramolecular selectivity (o, m, p distribution) to similar degrees. A mechanism is proposed in which both selectivities are determined by activation energy differences in the transition states leading to the σ-complex intermediates. The observation that most standard Friedel-Crafts benzylations do not follow the BSR is discussed in terms of possible systematic errors in those cases. Silver ion-assisted Friedel-Crafts benzylations were performed under dry, basic conditions to investigate whether the standard approach could lead to data that obey the BSR.
A Study of Essentially Free Carbocations Derived via Diazonium and Oxo Diazonium Ions in the Liquid Phase
Darbeau, Ron W.,White, Emu H.,Song, Fenhong,Darbeau, Nyla R.,Chou, James
, p. 5966 - 5978 (2007/10/03)
Nitrogen- and nitrous oxide-separated ion pairs containing 4-substituted benzyl cations and carboxylate or tosylate anions were prepared by thermolysis of N-nitroso- and N-nitroamides, acidification of phenyldiazomethane, and nitrosation of N-benzyl-O-benzoylhydroxylamine. The cations were generated in benzene/toluene and benzene/anisole mixtures and were found to partition between the counterion and the solvent and between the aromatic cosolvent and benzene. A familial relationship among the methods was observed. As the cation became more reactive, the yield of solvent-derived products (SDPs) rose and the ratio of rate constants for its reaction with toluene versus benzene, kT/kB, fell. The yield of SDP also rose as the temperature was decreased and as N2 was replaced by N2O; however, kT/kB remained unchanged. Inert diluents had no effect on kT/kB but decreased hydrocarbon yield by 40% on 2-fold dilution. In the presence of reactive diluents that are converted into secondary alkylating agents, both the % hydrocarbon and kT/kB rose. These results are interpreted in terms of the intermediacy of inert-molecule-separated ion pairs (IMSIPs) in deamination. The cation reacted with benzoates and tosylates not only at the oxygens but also at the ipso carbon; subsequent decarboxylation and desulfonylation, respectively, led to diphenylmethanes. The ester/SDP ratio is introduced as a new measure of carbocation reactivity.
ARYLALKYLATION OF 4-tert-BUTYLTOLUENE WITH SUBSTITUTED BENZYL CHLORIDES
Pozdnyakovich, Yu. V.,Savyak, R. P.,Shein, S. M.
, p. 522 - 526 (2007/10/02)
The reaction of 4-alkylbenzyl chlorides with 4-tert-butyltoluene in the presence of titanium tetrachloride and ferric chloride leads to the formation of 2-methyl-4'-alkyl-5-tert-butyldiphenylmethanes.The arylalkylation of 4-tert-butyltoluene with 2- and 4-chlorobenzyl chlorides, catalyzed by titanium tetrachloride, leads to the formation of mixtures of 2-methyl-5-tert-butyldiphenylmethane, 2-tert-butyl-5-methyldiphenylmethane, and isomeric methyldiphenylmethanes containing a chloride atom in the benzyl fragment.The products of the reaction catalyzed by ferric chloride do not contain 2-tert-butyl-5-methylchlorodiphenylmethanes.The reacti on of 4-nitrobenzyl chloride with 4-tert-butyltoluene in the presence of ferric chloride leads to the formation of a mixture of 2-methyl-4'-nitro-5-tert-butyldiphenylmethane and isomeric methylnitrodiphenylmethanes.Under the influence of AlCl3-CH3NO2 in benzene 2,4'-dimethyl-5-tert-butyldiphenylmethane eliminates both the 4-methylbenzyl group and the tert-butyl group.Under analogous conditions 2-methyl-5-tert-butyldiphenylmethanes containing a chlorine atom or a nitro group in the benzyl fragment are dealkylated with the elimination of only the tert-butyl group.
