1530-20-7Relevant academic research and scientific papers
Fluorous tin hydrides: A new family of reagents for use and reuse in radical reactions
Curran, Dennis P.,Hadida, Sabine,Kim, Sun-Young,Luo, Zhiyong
, p. 6607 - 6615 (1999)
Eight members of a new family of highly fluorinated (fluorous) tin hydrides have been synthesized and studied as reagents for radical reactions. Tin hydrides of the general formulas [Rf(CH2)n]3SnH and [Rf-(CH2)
Rate constants for reaction of a fluorous tin hydride reagent with primary alkyl radicals
Horner, John H.,Martinez, Felix N.,Newcomb, Martin,Hadida, Sabine,Curran, Dennis P.
, p. 2783 - 2786 (1997)
Rate constants for 6-exo cyclization of the 7,7-diphenyl-6-heptenyl radical (3) in benzotrifluoride (BTF, PhCF3) were determined by laser flash photolysis, and radical clock 3 was used in competition kinetic studies for determination of rate co
A new class of chiral organogermanes derived from C2-symmetric dithiols: Synthesis, characterization and stereoselective free radical reactions
Gualtieri, Giovanna,Geib, Steven J.,Curran, Dennis P.
, p. 5013 - 5019 (2003)
A new class of dithiostannanes and dithiogermanes have been prepared from 1,1′-binaphthyl-2,2′-dithiol and 3,3′-bis(trimethylsilyl)-1,1′ -binaphtho-2,2′-dithiol. While reduction of 4-butyl-4-chloro-3,5-dithia-4-stanna-cyclohepta[2,1-a;3,4- a′]dinaphthalen
Alkene homologation: via visible light promoted hydrophosphination using triphenylphosphonium triflate
Levin, Vitalij V.,Dilman, Alexander D.
supporting information, p. 749 - 752 (2021/02/03)
A hydrophosphination reaction of alkenes with triphenylphosphonium triflate under photocatalytic conditions is described. The reaction is promoted by naphthalene-fused N-acylbenzimidazole and is believed to proceed through intermediate formation of a phosphinyl radical cation. The resulting phosphonium salts are directly involved in the Wittig reaction leading to homologated alkenes.
Microwave-assisted periselective annulation of triarylphosphenes with aldehydes and ketones
Du, Changle,Fu, Xingyang,Fu, Zhicheng,Luo, Yun,Xu, Jiaxi
, p. 9526 - 9537 (2020/12/15)
The reaction of diazo(aryl)methyl(diaryl)phosphine oxides with aldehydes and ketones generates benzo-δ-phosphinolactones in low to good yields with 1,1-diarylalk-1-enes as byproducts under microwave irradiation. Diazo(aryl)methyl(diaryl)phosphine oxides first undergo a Wolff rearrangement to form diaryl(aryl)phosphenes, which further react with aldehydes and ketones to afford benzo-δ-phosphinolactones and β-phosphinolactones. The latter are unstable under heating and fragment into the corresponding 1,1-diarylalk-1-enes and arylphosphine dioxides under reaction conditions. The arylphosphine dioxides become arylphosphonic acids during workup. The periselectivity in the annulation shows that the reaction of diaryl(aryl)phosphenes with most aldehydes and ketones favors phosphene phenyl participation in (4 + 2) annulation(2 + 2) annulation. This journal is
Nickel-catalyzed alkylative cross-coupling of anisoles with grignard reagents via C-O bond activation
Tobisu, Mamoru,Takahira, Tsuyoshi,Morioka, Toshifumi,Chatani, Naoto
supporting information, p. 6711 - 6714 (2016/06/14)
We report nickel-catalyzed cross-coupling of methoxyarenes with alkylmagnesium halides, in which a methoxy group is eliminated. A wide range of alkyl groups, including those bearing β-hydrogens, can be introduced directly at the ipso position of anisole derivatives. We demonstrate that the robustness of a methoxy group allows this alkylation protocol to be used to synthesize elaborate molecules by combining it with traditional cross-coupling reactions or oxidative transformation. The success of this method is dependent on the use of alkylmagnesium iodides, but not chlorides or bromides, which highlights the importance of the halide used in developing catalytic reactions using Grignard reagents.
Synthetic utility of tribenzyltin hydride and its derivatives as easily accessible, removable, and decomposable organotin reagents
Yamakawa, Takeshi,Kinoshita, Hidenori,Miura, Katsukiyo
supporting information, p. 129 - 134 (2013/03/13)
Radical reactions using tribenzyltin hydride (Bn3SnH) easily prepared from tin and benzyl chloride were studied. The Et3B- initiated reduction and cyclization of haloalkanes and haloalkenes with Bn 3SnH proceeded efficiently. Homolytic hydrostannylation of alkynes with Bn3SnH followed by treatment with electrophiles gave functionalized alkenes in good to high yields. The organotin byproducts formed could be easily removable by filtration and silica-gel column chromatography without any pretreatment. It was also found that tribenzyltin chloride (Bn 3SnCl) easily decomposed to benzyl alcohol in a basic solution of H2O2.
Synthetic radical reactions using dibutylchlorogermane and dibutylethoxygermane as radical mediators
Miura, Katsukiyo,Ootsuka, Kazunori,Hosomi, Akira
, p. 3151 - 3153 (2007/10/03)
In the presence of Et3B as radical initiator, dibutylchlorogermane (1a) and dibutylethoxygermane (1b) reacted with bromo- and iodoalkanes at room temperature to give the corresponding alkanes in high yields. Hydrogermane 1a was more reactive than 1b. However, 1b worked as a better radical mediator in intermolecular radical addition of haloalkanes to electron-deficient alkenes. Georg Thieme Verlag Stuttgart.
Adjusting the top end of the alkyl radical kinetic scale. Laser flash photolysis calibrations of fast radical clocks and rate constants for reactions of benzeneselenol
Newcomb,Choi,Horner
, p. 1225 - 1231 (2007/10/03)
Rate constants for 5-exo cyclizations of the 6,6-diphenyl-5-hexenyl radical (1a), the 1-methyl-6,6-diphenyl-5-hexenyl radical (1b), and the 1,1- dimethyl-6,6-diphenyl-5-hexenyl radical (1c) were measured by laser flash photolysis methods, and Arrhenius parameters for these cyclizations were determined. Relative rate constants for cyclizations of radicals 1 and reactions with benzeneselenol were determined by indirect kinetic methods, and the relative Arrhenius parameters for the competing reactions were combined with the parameters for the cyclization reactions to give absolute Arrhenius parameters for the PhSeH reactions. At 20 °C, PhSeH reacts with the 1°, 2°, and 3°radicals 1 with nearly the same rate constants, (1.2 ± 0.1) x 109 M-1 s-1. Absolute Arrhenius parameters for reactions of PhSH and t-BuSH with the primary alkyl radical 1a were calculated using literature values for the competition between cyclization of 1a and reactions with the appropriate thiol and the absolute values for cyclization of 1a determined in this work. The results suggest that rate constants for reactions of primary alkyl radicals with t-BuSH are about 20% smaller than those previously reported. In the case of PhSH, the results are in good agreement with one previously reported set of rate constants but about 35% smaller than another set of rate constants that was subsequently incorporated into fast alkyl radical kinetics. The rate constants for alkyl radical reactions calibrated by competition against reaction with PhSeH and PhSH apparently are 30-40% smaller than those previously reported, and the derived rate constants for the fast radical reactions should be adjusted. An especially noteworthy example is ring opening of the cyclopropylcarbinyl radical, the Arrhenius function for which was determined in part from PhSH trapping results. Using the adjusted rate constants for PhSH and recalculating the Arrhenius parameters for the cyclopropylcarbinyl radical ring opening gives log(k/s- 1) = (13.045 ± 0.10) (6.99 ± 0.09)/θ (kcal/mol, errors at 2σ); the rate constant at 20 °C of 6.7 x 107 s-1 is about 13% smaller than that previously calculated.
Diamino compounds and methods for preparing them
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, (2008/06/13)
An object of the invention is to propose diamino compounds expressed by the following general formula (1) which are suitable to obtain a raw material, a polyimide resin, for a liquid crystal aligning film without any image sticking and with a high voltage holding ratio at from a low temperature to a high temperature as well as the preparation thereof: STR1
