144759-86-4Relevant articles and documents
Palladium-Catalyzed, Atmospheric Pressure Carbonylation of Allylic Halides under the Influence of Sodium Hydroxide or Alkoxides. A Facile Synthesis of β,γ-Unsaturated Acids
Okano, Tamon,Okabe, Nobuyuki,Kiji, Jitsuo
, p. 2589 - 2593 (1992)
The palladium-catalyzed, atmospheric-pressure carboxylation of allylic halides occurs readily in an aqueous sodium hydroxide/organic solvents two-phase system, giving β,γ-unsaturated acids.Phosphine complexes (I, L=m-(Ph2P)C6H4SO3Na; II, L=Ph3P) or Na2 (III) can be used as the catalyst.Atmospheric-pressure alkoxycarbonylation is realized under the influence of a homogeneous alcoholic solution of sodium alkoxide.Phosphine-free palladium complexes, such as 2 or III, are the favored catalyst. β,γ-Unsaturated esters are obtained in high yields.
Monoallylation and benzylation of dicarbonyl compounds with alcohols catalysed by a cationic cobalt(iii) compound
Chandra Sau, Mohan,Mandal, Smita,Bhattacharjee, Manish
, p. 9235 - 9245 (2021/03/16)
Monoallylation and monoalkylation of diketones and β-keto esters with allylic and benzylic alcohols catalysed by [Cp*Co(CH3CN)3][SbF6]2(I) are reported. The method does not require any additive and affords regioselective products. The mechanistic investigations were done byin situ1H NMR spectroscopy as well as control experiments. It has been shown that reactions proceedviaη3-allyl complex formation or ally ether intermediate. The alkylation takes placeviaonly ether intermediate. The resulting allylated and alkylated products have been used for the synthesis of eleven new trisubstituted pyrazoles and one pyrazolone.
Palladium-Catalyzed Allyl-Allyl Reductive Coupling of Allylamines or Allylic Alcohols with H2as Sole Reductant
Zhou, Xibing,Zhang, Guoying,Huang, Renbin,Huang, Hanmin
supporting information, p. 365 - 369 (2021/01/26)
Catalytic carbon-carbon bond formation building on reductive coupling is a powerful method for the preparation of organic compounds. The identification of environmentally benign reductants is key for establishing an efficient reductive coupling reaction. Herein an efficient strategy enabling H2 as the sole reductant for the palladium-catalyzed allyl-allyl reductive coupling reaction is described. A wide range of allylamines and allylic alcohols as well as allylic ethers proceed smoothly to deliver the C-C coupling products under 1 atm of H2. Kinetic studies suggested that the dinuclear palladium species was involved in the catalytic cycle.
Radical-Cation Cascade to Aryltetralin Cyclic Ether Lignans Under Visible-Light Photoredox Catalysis
Wang, Qian,Xiang, Jia-Chen,Zhu, Jieping
supporting information, p. 21195 - 21202 (2020/09/17)
The development of concise, sustainable, and cost-effective synthesis of aryltetralin lignans, bearing either a fused lactone or cyclic ether, is of significant medicinal importance. Reported is that in the presence of Fukuzumi's acridinium salt under blue LED irradiation, functionalized dicinnamyl ether derivatives are converted into aryltetralin cyclic ether lignans with concurrent generation of three stereocenters in good to high yields with up to 20:1 diastereoselectivity. Oxidation of an alkene to the radical cation is key to the success of this formal Diels–Alder reaction of electronically mismatched diene and dienophile. Applying this methodology, six natural products, aglacin B, aglacin C, sulabiroin A, sulabiroin B, gaultherin C, and isoshonanin, are synthesized in only two to three steps from readily available biomass-derived monolignols. A revised structure is proposed for gaultherin C.
Method for synthesizing ether by catalyzing alcohol through trimethyl halosilane
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Paragraph 0063-0066, (2020/12/29)
The invention discloses a method for synthesizing ether by catalyzing alcohol through trimethyl halosilane. According to the method, under the conditions of air or nitrogen atmosphere, no solvent andno transition metal catalyst, an alcohol compound is directly used as a raw material, trimethyl halosilane is used as a catalyst, and symmetric or asymmetric ether is synthesized through one-step selective dehydration reaction. According to the method, the use of strong acid, strong base and organic primary halides with high toxicity, instability and higher price is avoided, the synthesis steps are shortened, the synthesis efficiency is improved, the reaction has good selectivity, and a target ether product can be obtained preferentially.
Gold(I)/Chiral N,N′-Dioxide–Nickel(II) Relay Catalysis for Asymmetric Tandem Intermolecular Hydroalkoxylation/Claisen Rearrangement
Li, Jun,Lin, Lili,Hu, Bowen,Zhou, Pengfei,Huang, Tianyu,Liu, Xiaohua,Feng, Xiaoming
supporting information, p. 885 - 888 (2017/01/13)
A highly efficient asymmetric cascade reaction between alkynyl esters and allylic alcohols has been realized. Key to success was the combination of a hydroalkoxylation reaction catalyzed by a π-acidic gold(I) complex with a Claisen rearrangement catalyzed by a chiral Lewis acidic N,N′-dioxide–nickel(II) complex. A range of acyclic α-allyl β-keto esters were synthesized in high yields (up to 99 %) with good diastereoselectivities (up to 97:3) and excellent enantioselectivities (up to 99 % ee) under mild reaction conditions. These products can be easily transformed into optically active β-hydroxy esters, β-hydroxy acids, or 1,3-diols.
Continuous-Flow Multistep Synthesis of Cinnarizine, Cyclizine, and a Buclizine Derivative from Bulk Alcohols
Borukhova, Svetlana,Nol, Timothy,Hessel, Volker
, p. 67 - 74 (2016/01/16)
Cinnarizine, cyclizine, buclizine, and meclizine belong to a family of antihistamines that resemble each other in terms of a 1-diphenylmethylpiperazine moiety. We present the development of a four-step continuous process to generate the final antihistamines from bulk alcohols as the starting compounds. HCl is used to synthesize the intermediate chlorides in a short reaction time and excellent yields. This methodology offers an excellent way to synthesize intermediates to be used in drug synthesis. Inline separation allows the collection of pure products and their immediate consumption in the following steps. Overall isolated yields for cinnarizine, cyclizine, and a buclizine derivative are 82, 94, and 87 %, respectively. The total residence time for the four steps is 90 min with a productivity of 2 mmol h-1. The incredible bulk: Bulk alcohols are converted continuously into chlorides using HCl in a microflow. A reaction network that consists of four steps and two inline separations leads to the continuous preparation of cinnarizine, cyclizine, and a buclizine derivative with yields of 82, 94, and 87 %, respectively. The total residence time for the four steps is 90 min with a productivity of 2 mmol h-1.
Organohalide-catalyzed dehydrative O-alkylation between alcohols: A facile etherification method for aliphatic ether synthesis
Xu, Qing,Xie, Huamei,Chen, Pingliang,Yu, Lei,Chen, Jianhui,Hu, Xingen
supporting information, p. 2774 - 2779 (2015/05/27)
Organohalides are found to be effective catalysts for dehydrative O-alkylation reactions between alcohols, providing selective, practical, green, and easily scalable homo- and cross-etherification methods for the preparation of useful symmetrical and unsymmetrical aliphatic ethers from the readily available alcohols. Mechanistic studies revealed that organohalides are regenerated as reactive intermediates and recycled to catalyze the reactions.
Moisture-Tolerant Frustrated Lewis Pair Catalyst for Hydrogenation of Aldehydes and Ketones
Gy?m?re, ádám,Bakos, Mária,F?ldes, Tamás,Pápai, Imre,Domján, Attila,Soós, Tibor
, p. 5366 - 5372 (2015/09/15)
In this paper, we report on the development of a bench-stable borane for frustrated Lewis pair catalyzed reduction of aldehydes, ketones, and enones. The deliberate fine-tuning of structural and electronic parameters of Lewis acid component and the choice of Lewis base provided for the first time, a moisture-tolerant FLP catalyst. Related NMR and DFT studies underpinned the unique behavior of this FLP catalyst and gave insight into the catalytic activity of the resulting FLP catalyst.
Dehydrative cross-coupling reactions of allylic alcohols with olefins
Gumrukcu, Yasemin,De Bruin, Bas,Reek, Joost N. H.
supporting information, p. 10905 - 10909 (2014/09/17)
The direct dehydrative activation of allylic alcohols and subsequent cross-coupling with alkenes by using palladium catalyst containing a phosphoramidite ligand is described. The activation of the allyl alcohol does not require stoichiometric additives, thus allowing clean, waste-free reactions. The scope is demonstrated by application of the protocol to a series allylic alcohols and vinyl arenes, leading to variety of 1,4-diene products. Based on kinetic studies, a mechanism is proposed that involves a palladium hydride species that activates the allyl alcohol to form the allyl intermediate.
