93645-90-0Relevant academic research and scientific papers
Light/Palladium-Promoted Benzylic C?H Acylation Using a Benzoyl Group as the Photo-Directing Group
Masuda, Yusuke,Ishida, Naoki,Murakami, Masahiro
, p. 403 - 406 (2019/01/22)
2-Methylphenyl ketones undergo site-selective acylation at the benzylic position when treated with acid anhydride under UV irradiation in the presence of a palladium catalyst. The benzoyl carbonyl group serves as the photo-directing group so that the ortho benzylic C?H bond is activated site-selectively.
Intermolecular Dehydrative Coupling and Intramolecular Cyclization of Ruthenium Vinylidene Complexes Formed from Aromatic Propynes Containing Carbonyl Functionalities
Chia, Pi-Yeh,Kuo, Cheng-Chen,Huang, Shou-Ling,Liu, Yi-Hong,Liu, Ling-Kang,Lin, Ying-Chih
, p. 3885 - 3894 (2018/11/10)
A remarkable intermolecular dehydrative coupling reaction with the formation of a C?C bond was found for the vinylidene complex 2 a, yielding the dinuclear bisvinylidene complex 4 a. Complex 2 a containing 1-hydroxyindan moiety was first formed from the reaction of o-propynyl benzaldehyde 1 a with [Ru]–Cl ([Ru]=Cp(PPh3)2Ru) by a cyclization process. For analogous aldehyde 1 b containing an additional 1,3-dioxolane group on the aryl ring, similar intermolecular coupling yields the dinuclear bisvinylidene complex 4 b. However, the fluoro group on the aryl ring in aldehyde 1 c inhibits the coupling reaction, giving only the vinylidene complex 2 c. For the reactions of [Ru]–Cl in MeOH with compounds 1 f, 1 g and 1 h, each with a ketone functionality, cyclization gives vinylidene complexes 2 f, 2 g and 2 h, respectively. However, no similar intermolecular coupling was observed, instead, the intramolecular dehydration yields 8 f, 8 g and 8 h, respectively. In CDCl3, catalytic cyclization is observed for the o-propynylphenyl ketone 1 h with [Ru]–Cl at 50 °C giving the isochromene products 14 h. Furthermore, treatment of the o-propynylaryl α,β-unsaturated ketones 1 k–m and 1 n with [Ru]–Cl in MeOH affords the corresponding vinylidene complexes 10 k–m and 11 n each with 1-benzosuberone moiety in the presence of NH4PF6. These intramolecular cyclization products were formed by the addition of Cβ onto the terminal carbon of the alkene moiety. All these reaction products were characterized by spectroscopic methods. In addition, structures of complexes 4 a, and 10 l were confirmed by single crystal X-ray diffraction analysis.
Salicylic Acid-Catalyzed Arylation of Enol Acetates with Anilines
Felipe-Blanco, Diego,Gonzalez-Gomez, Jose C.
supporting information, p. 2773 - 2778 (2018/07/29)
α-Aryl ketones are both structure moieties commonly found in bioactive compounds and versatile synthetic intermediates for the preparation of drug-like molecules. An operationally simple and scalable protocol has been developed to prepare α-aryl ketones from readily available aromatic amines and enol acetates (or silyl enol ethers). This metal-free methodology features the use of salicylic acid as a convenient catalyst to promote the formation of aryl radicals from in-situ generated aryl diazonium salts, without demanding thermal or photochemical activation. The mild reaction conditions used are compatible with anilines substituted with diverse functionalities. Structural elaboration of some prepared α-aryl ketones was accomplished to illustrate their usefulness as building blocks. (Figure presented.).
Enantioselective Synthesis of 1,2-Dihydronaphthalenes via Oxidative N-Heterocyclic Carbene Catalysis
Perveen, Saima,Zhao, Zhifei,Zhang, Guoxiang,Liu, Jian,Anwar, Muhammad,Fang, Xinqiang
, p. 2470 - 2473 (2017/05/24)
1,2-Dihydronaphthalenes are important molecules in both medicinal and synthetic chemistry, but methods for the catalytic asymmetric construction of this class of molecules are limited. The diastereo- and enantioselective N-heterocyclic carbene-catalyzed cascade annulation reactions using benzodiketones and enals under oxidative conditions, which afford a variety of 1,2-dihydronaphthalenes with two adjacent stereocenters in up to 99% yield, with >20:1 dr, and up to 99% ee, are reported. Furthermore, the product can be easily transformed to a series of useful compounds such as alcohol, amide, and epoxide.
Synthesis of 2,3-benzodiazepines and 2,3-benzodiazepin-4-ones from arynes and β-diketones
Okuma, Kentaro,Tanabe, Yukiko,Nagahora, Noriyoshi,Shioji, Kosei
, p. 1064 - 1073 (2015/09/01)
2,3-Benzodiazepines were synthesized by two-step or one-pot reactions from aryne precursors. Reaction of 2- (trimethylsilyl)aryl triflates with β-diketones in the presence of CsF gave ortho-substituted benzophenones. Treatment of benzophenones with hydrazine hydrate resulted in the formation of 2,3-benzodiazepines in moderate yields. Tofisopam, a well known anxiolytic, could be synthesized via C-C bond insertion of 3,4-dimethoxybenzyne with 2-ethyl-1-(3,4-dimethoxyphenyl)butane-1,3-dione, followed by the reaction with hydrazine hydrate in one-pot operation. 2,3-Benzodiazepin-4-ones were also synthesized by the reaction of β-keto esters with triflates in the presence of CsF, followed by the addition of hydrazine hydrate. Substituted isoquinolines were synthesized by the reaction of ortho-substituted benzophenones with ammonium hydroxide.
Enantioselective Synthesis of 4,4′-Biaryl-BINOLs from Arynes and β-Diketones
Okuma, Kentaro,Horigami, Kenta,Nagahora, Noriyoshi,Shioji, Kosei
, p. 2937 - 2944 (2015/09/28)
The reaction of 2-(trimethylsilyl)phenyl triflate with aroylacetones in the presence of CsF gave the corresponding 4-aryl-2-naphthols. Substituted triflates also reacted with aroylacetones to afford 4-aryl-2-naphthols regioselectively. The enantioselectiv
Tandem carbon-carbon bond insertion and intramolecular aldol reaction of benzyne with aroylacetones: Novel formation of 4,4′-disubstituted 1,1′-binaphthols
Okuma, Kentaro,Itoyama, Ryoichi,Sou, Ayumi,Nagahora, Noriyoshi,Shioj, Kosei
, p. 11145 - 11147 (2013/01/15)
An efficient route to 4-aryl-2-naphthols from arynes and aroylacetones was developed by carbon-carbon bond insertion followed by an intramolecular aldol reaction and dehydration. Benzyne derived from 2-(trimethylsilyl)phenyl triflate reacted with benzoyla
Yanovsky Reaction of η6-Arene-η5-cyclopentadienyliron Cations with Carbanions derived from Ketones. Regiospecific Attack ortho to Electron Withdrawing Functions
Sutherland, Ronald G.,Chowdhury, Ratan L.,Piorko, Adam,Lee, Choi Chuck
, p. 1296 - 1297 (2007/10/02)
η6-Arene-η5-cyclopentadienyliron salts containing electron withdrawing groups such as nitro, halogeno, benzoyl, cyano, and sulphonyl on the arene ring react with carbanions to give electroneutral adducts of the Yanovsky type; these a
