1520-39-4Relevant academic research and scientific papers
Decarboxylative Cross-Electrophile Coupling of N-Hydroxyphthalimide Esters with Aryl Iodides
Huihui, Kierra M. M.,Caputo, Jill A.,Melchor, Zulema,Olivares, Astrid M.,Spiewak, Amanda M.,Johnson, Keywan A.,Dibenedetto, Tarah A.,Kim, Seoyoung,Ackerman, Laura K. G.,Weix, Daniel J.
, p. 5016 - 5019 (2016/05/19)
A new method for the decarboxylative coupling of alkyl N-hydroxyphthalimide esters (NHP esters) with aryl iodides is presented. In contrast to previous studies that form alkyl radicals from carboxylic acid derivatives, no photocatalyst, light, or arylmetal reagent is needed, only nickel and a reducing agent (Zn). Methyl, primary, and secondary alkyl groups can all be coupled in good yield (77% ave yield). One coupling with an acid chloride is also presented. Stoichiometric reactions of (dtbbpy)Ni(2-tolyl)I with an NHP ester show for the first time that arylnickel(II) complexes can directly react with NHP esters to form alkylated arenes.
Copper-Catalyzed Boron-Selective C(sp2)-C(sp3) Oxidative Cross-Coupling of Arylboronic Acids and Alkyltrifluoroborates Involving a Single-Electron Transmetalation Process
Ding, Siyi,Xu, Liang,Li, Pengfei
, p. 1329 - 1333 (2016/02/18)
A rapid and highly selective oxidative cross-coupling reaction between readily available and shelf-stable arylboronic acids and primary or secondary potassium alkyltrifluoroborates was devised and developed, which works under mild conditions using copper(II) acetate as the catalyst and silver oxide as the oxidant. Initial experimental results indicate that a single-electron transmetalation process is involved. This approach effectively bypasses the problems associated with the traditional cross-coupling reactions of alkylboronates and thus provides a complementary method in building C(sp2)-C(sp3) bonds.
Indium(III)-catalyzed reductive monoalkylation of electron-rich benzenes with aliphatic carboxylic acids leading to arylalkane derivatives
Moriya, Toshimitsu,Takayama, Kentaro,Konakahara, Takeo,Ogiwara, Yohei,Sakai, Norio
supporting information, p. 2277 - 2281 (2015/03/31)
Described herein is the reaction of electron-rich aromatic compounds with aliphatic carboxylic acids treated with a catalytic amount (5 mol-%) of InI3, 1,1,3,3-tetramethyldisiloxane (TMDS), and molecular iodine. The reductive monoalkylation occurs smoothly to produce the corresponding arylalkane derivatives.
Acceleration of CuI-catalyzed coupling reaction of alkyl halides with aryl Grignard reagents using lithium chloride
Nakata, Kenya,Feng, Chao,Tojo, Toshifumi,Kobayashi, Yuichi
supporting information, p. 5774 - 5777 (2014/12/11)
In the presence of LiCl, CuI-catalyzed coupling reaction of R(alkyl)-X with Ar(aryl)MgBr at rt was completed within 2 h. Effective leaving groups X in R-X were Br, I, OTs, but not Cl. Grignard reagents ArMgBr with both standard and bulky Ar such as 2-MeC
Branched and Star-Branched Styrene Polymers, Telomers, and Adducts, Their Synthesis, Their Bromination, and Their Uses
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, (2011/10/04)
New branched or star-branched styrene polymeric, telomeric, and monomeric product distributions, their preparation, their use as raw materials for bromination to produce flame retardants, the flame retardants themselves, and their use as flame retardants
Cation-π interactions in the gas phase methylation of α,ωdiphenylalkanes
Chiavarino, Barbara,Crestoni, Maria E.,Fornarini, Simonetta,Kuck, Dietmar
, p. 4619 - 4624 (2007/10/03)
The methylation of α,ω-diphenylalkanes (C6H5(CH2)nC6H5 , n = 1-6) has been performed in the gas phase using Me2Cl+ ions as alkylating species and toluene as reference substrate. Both in radiolytic experiments at atmospheric pressure and in FT-ICR measurements at 10-8 Torr, the selected diphenylalkanes reacted faster than toluene, the highest reactivity displayed by 1,3-diphenylpropane. The kinetic pattern of the reaction, conforming to the established scheme of an electrophilic alkylation reaction, is consistent with a rate-determining formation of the σ-complex intermediate, at variance with the tert-butylation of the same series of compounds by Me3C+ ions, occurring at the collisional encounter rate. The kinetic features are explained by a marked effect due to the presence of the second aryl ring, providing additional stabilization of both the ion-neutral collision complex and the σ complex with respect to toluene. Both factors contribute to the δEa of ca. 8 kcal mol-1 for the competition of 1,3-diphenylpropane and toluene found in the temperature dependence study of the Me2Cl+ reaction.
Boronic acids: New coupling partners in room-temperature Suzuki reactions of alkyl bromides. Crystallographic characterization of an oxidative-addition adduct generated under remarkably mild conditions
Kirchhoff, Jan H.,Netherton, Matthew R.,Hills, Ivory D.,Fu, Gregory C.
, p. 13662 - 13663 (2007/10/03)
The Suzuki reaction is an exceptionally useful cross-coupling process that has been widely applied in synthetic chemistry, and boronic acids are, by far, the most commonly employed coupling partner. To date, however, no versatile method has been developed for cross-coupling boronic acids with unactivated alkyl (as opposed to aryl or vinyl) electrophiles. This report describes a catalyst system that achieves this objective at room temperature. On the mechanistic side, this study demonstrates that Pd(P(t-Bu)2Me)2 undergoes oxidative addition under surprisingly mild conditions (0 °C). The resulting adduct is sufficiently stable toward β-hydride elimination that it can be structurally characterized, and it is a chemically competent intermediate in the cross-coupling process. Copyright
The gas-phase reactivity of p-Me3Si-substituted 1,3-diphenylpropane towards charged electrophiles: Intra- and interannular hydrogen migrations
Crestoni, Maria Elisa
, p. 993 - 999 (2007/10/03)
The gas-phase reaction of p-Me3SiC6H4(CH2)3C6H5 (p-TSDPP) with gaseous cations, including C2H5+, Me2Cl+ and DCO+, has been studied in the pressure range from 10-8 to 103 Torr by Fourier-transform ion cyclotron resonance (FT-ICR) and by the radiolytic technique. The protonated or alkylated intermediates undergo intramolecular migration and intermolecular transfer of protons and/or Me3Si+. The results underline the role of the spectator ring in providing internal solvation to an arenium moiety, as evidenced by the noticeable stability towards Me3Si loss with respect to a single-ring model substrate, p-Me3SiC6H4Me (p-TST), upon reaction with the same gaseous ions. The extent of the alkylation route relative to the alkyldesilylation processes, measured as a function of the arenium ion lifetime, permits derivation of the rate constant for the conversion by proton transfer of the originally formed arenium ions to ipso-silylated isomers (k(i)). The estimated values of k(i(p-TST)) = 5 x 109 s-1 and k(i(p-TSDPP)) = 2 x 108 s-1 at 120°C suggest that interannular H shifts are faster than ring-to-ring H transfer, in agreement with previous evidence from tert-butylated arenium ions. The reactivity of [Me3Si=arene]+ adducts, adequately described by the Wheland σ-complex model, does not exclude the intermediacy of an ion-neutral noncovalent complex.
