104-72-3Relevant academic research and scientific papers
Nickel-catalysed anti-Markovnikov hydroarylation of unactivated alkenes with unactivated arenes facilitated by non-covalent interactions
Hartwig, John F.,Nakao, Yoshiaki,Ohgi, Akito,Saper, Noam I.,Semba, Kazuhiko,Small, David W.
, (2020)
Anti-Markovnikov additions to alkenes have been a longstanding goal of catalysis, and anti-Markovnikov addition of arenes to alkenes would produce alkylarenes that are distinct from those formed by acid-catalysed processes. Existing hydroarylations are either directed or occur with low reactivity and low regioselectivity for the n-alkylarene. Herein, we report the first undirected hydroarylation of unactivated alkenes with unactivated arenes that occurs with high regioselectivity for the anti-Markovnikov product. The reaction occurs with a nickel catalyst ligated by a highly sterically hindered N-heterocyclic carbene. Catalytically relevant arene- and alkene-bound nickel complexes have been characterized, and the rate-limiting step was shown to be reductive elimination to form the C–C bond. Density functional theory calculations, combined with second-generation absolutely localized molecular orbital energy decomposition analysis, suggest that the difference in activity between catalysts containing large and small carbenes results more from stabilizing intramolecular non-covalent interactions in the secondary coordination sphere than from steric hindrance.
Photoinduced Charge-Transfer State of 4-Carbazolyl-3-(trifluoromethyl)benzoic Acid: Photophysical Property and Application to Reduction of Carbon?Halogen Bonds as a Sensitizer
Matsubara, Ryosuke,Shimada, Toshiyuki,Kobori, Yasuhiro,Yabuta, Tatsushi,Osakai, Toshiyuki,Hayashi, Masahiko
, p. 2006 - 2010 (2016)
The photoinduced persistent intramolecular charge-transfer state of 4-carbazolyl-3-(trifluoromethyl)benzoic acid was confirmed. It showed a higher catalytic activity in terms of yield and selectivity in the photochemical reduction of alkyl halides compared to the parent carbazole. Even unactivated primary alkyl bromides could be reduced by this photocatalyst. The high catalytic activity is rationalized by considering the slower backward single-electron transfer owing to the spatial separation of the donor and acceptor subunits.
A catalytic C-C bond-forming reaction between aliphatic fluorohydrocarbons and arylsilanes
Luehmann, Nicole,Panisch, Robin,Mueller, Thomas
, p. 533 - 537 (2010)
C-C coupling reactions between arylsilanes and alkylfluorides are efficiently catalyzed by disilyl cation 1. Primary as well as secondary alkylfluorides were quantitatively coupled with arylsilanes; however, in the case of tertiary fluorides, the hydrodef
A CONVENIENT REDUCTION OF DIALKYLATED TOSYLMETHYL ISOCYANIDE
Yadav, J. S.,Reddy, P. Satyanarayana
, p. 4025 - 4028 (1984)
Dialkylated tosylmethyl isocyanides have been conveniently reduced to the corresponding hydrocarbons with lithium in liquid ammonia.This process has been succesfully utilised in the synthesis of (Z)-9-tricosene - a sex pheromone of common house fly.
Cross-Coupling Reactions of Alkyl Halides with Aryl Grignard Reagents Using a Tetrachloroferrate with an Innocent Countercation
Hashimoto, Toru,Maruyama, Tsubasa,Yamaguchi, Takamichi,Matsubara, Yutaka,Yamaguchi, Yoshitaka
supporting information, p. 4232 - 4236 (2019/08/16)
Bis(triphenylphosphoranylidene)ammonium tetrachloroferrate, (PPN)[FeCl4] (1), was evaluated as a catalyst for cross-coupling reactions. 1 exhibits high stability toward air and moisture and is an effective catalyst for the reaction of secondary alkyl halides with aryl Grignard reagents. The PPN cation is considered as an innocent counterpart to the iron center. We have developed an easy-to-handle iron catalyst for “ligand-free” cross-coupling reactions. (Figure presented.).
Involving Single-Atom Silver(0) in Selective Dehalogenation by AgF under Visible-Light Irradiation
Wu, Wenli,Cui, Enxin,Zhang, Yun,Zhang, Chen,Zhu, Feng,Tung, Chen-Ho,Wang, Yifeng
, p. 6335 - 6341 (2019/07/04)
The dehalogenation-arylation and the hydrodehalogenation of various types of organic halides are selectively realized using AgF and visible light without any organic additives under mild conditions. Single-atom silver(0) (denoted as SAAg) serves as the catalytically active center, and the TOF of SAAg reaches 6000 h-1. This elusive activity of Ag is beyond that expected from its ionic, nano, or bulk forms.
Hexadecane Conversion on an Alumina–Nickel Catalyst
Chesnokov,Chichkan,Paukshtis,Chesalov, Yu. A.,Krasnov
, p. 439 - 445 (2019/09/04)
Abstract: The conversion of hexadecane on a 4% Ni/Al2O3 catalyst in a temperature range of 20–300°C was studied using IR spectroscopy and catalytic methods. It was found that the dehydrogenation of hexadecane occurred at 20–100°C with the subsequent formation of aromatic products, but the rates of these processes were very low. As the reaction temperature was increased to 200°C, the 4% Ni/Al2O3 catalyst exhibited a maximum activity and high selectivity for the formation of 1-hexadecene, and aromatic compounds and cracking products were present in the reaction products. As the reaction temperature was further increased, the catalytic activity significantly decreased. This was due to the fact that polyaromatic deposits gradually accumulated on the catalyst surface in a temperature range of 200–300°C.
Terminal C(sp3)–H alkylation of internal alkenes via Ni/H-catalyzed isomerization
Wang, Zhen-Yu,Wan, Jia-Hao,Wang, Gao-Yin,Wang, Rui,Jin, Ruo-Xing,Lan, Quan,Wang, Xi-Sheng
supporting information, p. 2302 - 2305 (2018/05/16)
An efficient nickel-catalyzed reductive relay cross-coupling of internal alkenes with alkyl (or aryl) halides has been developed. This method has demonstrated broad substrate scope, mild reaction conditions and excellent terminal-selectivity. Moreover, th
Cross-coupling reaction of alkyl halides with alkyl grignard reagents catalyzed by cp-iron complexes in the presence of 1,3-butadiene
Iwasaki, Takanori,Shimizu, Ryohei,Imanishi, Reiko,Kuniyasu, Hitoshi,Kambe, Nobuaki
supporting information, p. 763 - 766 (2018/05/29)
Iron-catalyzed cross-coupling reaction of alkyl halides with alkyl Grignard reagents by the combined use of cyclopentadienyl ligand and 1,3-butadiene additive is described. The reaction smoothly proceeds at room temperature using unactivated alkyl bromides and fluorides via non-radical mechanism, which is in sharp contrast with hitherto known Fe-catalyzed cross-coupling reactions of alkyl halides.
Alkyl diphenyl phosphine and preparing alkyl diphenyl phosphine payment proportional to production alkyl benzene
-
Paragraph 0067; 0070-0073, (2017/08/25)
The invention discloses alkyl diphenylphosphine and a method for preparing alkyl diphenylphosphine with co-production of alkylbenzene. The structural formula of alkyl diphenylphosphine is shown in a formula I. The method comprises: adding triphenylphosphine and metal lithium into an organic solvent for reaction for 3-6 hours at room temperature; and cooling the reaction system to 0-10 DEG C, adding halogenated straight-chain alkane for insulating reaction, then raising the temperature of the system to 30-80 DEG C, keeping the temperature to react for 1-3 hours, removing the organic solvent and reducing the pressure and distilling to separately obtain alkyl diphenylphosphine and alkylbenzene. According to the alkyl diphenylphosphine disclosed by the invention, alkyl is directly bonded with P, so that the alkyl diphenylphosphine can be dissolved in most solvents and can be used as a ligand for homogeneous catalysts. By virtue of the method disclosed by the invention, high value straight-chain alkylbenzene is co-produced while straight-chain alkyl diphenylphosphine is prepared by way of a one-pot process. Use of chloro-tert-butane which is relatively high in price and waste of the metal lithium are avoided. The method is simple to operate, efficient, low in energy consumption, low in cost and suitable for large-scaled industrial production.
