41652-86-2Relevant academic research and scientific papers
Dynamic Covalent Chemistry of Nucleophilic Substitution Component Exchange of Quaternary Ammonium Salts
Kulchat, Sirinan,Lehn, Jean-Marie
, p. 2484 - 2496 (2015/11/02)
Dynamic covalent libraries (DCLs) of quaternary ammonium cations were set up by reversible nucleophilic substitution (SN2′ and SN2) exchange reactions of ammonium salts and tertiary amines. The reactions were conducted at 60 °C to generate thermodynamically and kinetically controlled mixtures of quaternary ammonium compounds and tertiary amines, and were accelerated by using iodide as a nucleophilic catalyst. Microwave irradiation was used to assist the exchange reaction between the pyridinium salts and pyridine derivatives. Finally, experiments towards the generation of dynamic ionic liquids were performed. The results of this study pave the way for the extension of dynamic combinatorial chemistry to nucleophilic substitution reactions.
Palladium-catalyzed aerobic oxidative allylic C-H arylation of alkenes with polyfluorobenzenes
Jiang, Huanfeng,Yang, Wanfei,Chen, Huoji,Li, Jianxiao,Wu, Wanqing
supporting information, p. 7202 - 7204 (2014/07/07)
An aerobic oxidative cross-coupling reaction of alkenes with polyfluorobenzenes, through palladium-catalyzed allylic C-H activation, is reported. This attractive route provides a new way to forge allylic C-C bonds of valuable products, in good yields, with high regioselectivity.
Method for Allylating and Vinylating Aryl, Heteroaryl, Alkyl, and Alkene Halogenides Using Transition Metal Catalysis
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Paragraph 0062; 0063; 0064, (2013/07/25)
What is described is a process for preparing organic compounds of the general formula (I) R—R′??(I) by converting a corresponding compound of the general formula (II) R—X ??(II) in which X is fluorine, chlorine, bromine or iodine to an organomagnesium compound of the general formula (III) [M+]n[RmMgXkY1]??(III) wherein compounds of the formula (III) are reacted with a compound of the general formula (IV) characterized in that the reaction of (III) with (IV) is performed in the presence of a) catalytic amounts of an iron compound, based on the compound of the general formula (II), and optionally in the presence of b) a nitrogen-, oxygen- and/or phosphorus-containing additive in a catalytic or stoichiometric amount, based on the compound of the general formula (II).
Cross-coupling of aromatic bromides with allylic silanolate salts
Denmark, Scott E.,Werner, Nathan S.
supporting information; experimental part, p. 16382 - 16393 (2009/05/08)
The sodium salts of allyldimethylsilanol and 2-butenyldimethylsilanol undergo palladium-catalyzed cross-coupling with a wide variety of aryl bromides to afford allylated and crotylated arenes. The coupling of both silanolates required extensive optimization to deliver the expected products in high yields. The reaction of the allyldimethylsilanolate takes place at 85°C in 1,2-dimethoxyethane with allylpalladium chloride dimer (2.5 mol %) to afford 73-95% yields of the allylation products. Both electron-rich and sterically hindered bromides reacted smoothly, whereas electron-poor bromides cross-coupled in poor yield because of a secondary isomerization to the 1-propenyl isomer (and subsequent polymerization). The 2-butenyldimethylsilanolate (E/Z, 80:20) required additional optimization to maximize the formation of the branched (γ-substitution) product. A remarkable influence of added alkenes (dibenzylideneacetone and norbornadiene) led to good selectivities for electron-rich and electron-poor bromides in 40-83% yields. However, bromides containing coordinating groups (particularly in the ortho position) gave lower, and in one case even reversed, selectivity. Configurationally homogeneous (E)-silanolates gave slightly higher γ-selectivity than the pure (Z)-silanolates. A unified mechanistic picture involving initial γ-transmetalation followed by direct reductive elimination or σ-π isomerization can rationalize all of the observed trends.
Palladium-mediated intramolecular C-N bond formation between tertiary amines and alkenes
Van Der Schaaf, Paul A.,Sutter, Jean-Pascal,Grellier, Mary,Van Mier, Guido P. M.,Spek, Anthony L.,Van Koten, Gerard,Pfeffer, Michel
, p. 5134 - 5144 (2007/10/02)
The reaction of terminal alkenylarenes having either o-(dimethylamino) or o-[(dimethylamino)methyl] substituents with PdCl2(MeCN)2 in MeOH in the presence of NaOAc and PPh3 has been studied. This reaction affords allylic p
