- One-Pot Synthesis of 2-Aminobenzophenones from 2-Alkynyl Arylazides Catalyzed by Pd and Cu Precursors
-
We describe a novel one-pot three-step reaction of 2-alkynyl arylazides through palladium-catalyzed formation of 3-hydroxy-3-phenylindolin-2-ones followed by hydrolysis of amide bonds and copper-catalyzed decarboxylation to give 2-aminobenzophenones. This synthetic method works well with various 2-alkynyl arylazides and affords the products in moderate to good yields under mild reaction conditions.
- Fan, Hui,Xu, Shijie,Yang, Fan,Zhang, Xiaoxiang,Zhao, Xuechun
-
supporting information
p. 4555 - 4558
(2021/08/30)
-
- Synthesis of 1-Amino-2,2,2-trifluoroalkylphosphonates from Alkene-Tethered Trifluoroacetimidoyl Chlorides
-
The reaction of alkene-tethered trifluoroacetimidoyl chlorides with trialkyl phosphites furnishes 1-amino-2,2,2-trifluoroalkylphosphonates. The products were generated in moderate to good yields, and the scalability of this process was showcased. Partial hydrolysis of the phosphonate moiety was achieved. The cyclization is proposed to occur via formation of an imidoyl phosphonate intermediate that becomes susceptible to nucleophilic attack at nitrogen through the strong electron-withdrawing groups at the imidoyl carbon.
- Rodríguez, José F.,Zhang, Anji,Arora, Ramon,Lautens, Mark
-
supporting information
p. 7540 - 7544
(2021/10/12)
-
- Visible Light Induced Cyclization to Spirobi[indene] Skeletons from Functionalized Alkylidienecyclopropanes
-
In this paper, we revealed a metal-free and visible light photoinduced method for the rapid construction of spirobi[indene] skeletons, providing a simple and efficient way for easy access to spirobi[indene] scaffolds under mild conditions along with a broad substrate scope and good functional group tolerance.
- Li, Quanzhe,Liu, Jiaxin,Shi, Min,Wei, Yin
-
-
- Method for synthesizing ortho-amino aromatic ketone from aromatic carboxylic acid
-
Disclosed is a method for synthesizing ortho-amino aromatic ketone from aromatic carboxylic acid. The method comprises the steps that with 2-arylsulfonamido aromatic carboxylic acid shown in the description as a raw material and triphenylphosphine as a deoxidizer, under the illumination of blue light, in a 1,4-dioxane solution, under an argon atmosphere, in the presence of the dipotassium hydrogenphosphate, with [Ir(dF(CF3)ppy)2(dtbbpy)]PF6 as a photocatalyst, the ortho-amino aromatic ketone compound is obtained; the structure of the photocatalyst [Ir(dF(CF3)ppy)2(dtbbpy)]PF6 is shown in thedescription.
- -
-
Paragraph 0055; 0056
(2019/07/04)
-
- Deoxygenative Arylation of Carboxylic Acids by Aryl Migration
-
An unprecedented deoxygenative arylation of aromatic carboxylic acids has been achieved, allowing the construction of an enhanced library of unsymmetrical diaryl ketones. The synergistic photoredox catalysis and phosphoranyl radical chemistry allows for precise cleavage of a stronger C?O bond and formation of a weaker C?C bond by 1,5-aryl migration under mild reaction conditions. This new protocol is independent of substrate redox-potential, electronic, and substituent effects. It affords a general and promising access to 60 examples of synthetically versatile o-amino and o-hydroxy diaryl ketones under redox-neutral conditions. Furthermore, it also brings one concise route to the total synthesis of quinolone alkaloid, (±)-yaequinolone A2, and a viridicatin derivative in satisfying yields.
- Ruzi, Rehanguli,Ma, Junyang,Yuan, Xiang-Ai,Wang, Wenliang,Wang, Shanshan,Zhang, Muliang,Dai, Jie,Xie, Jin,Zhu, Chengjian
-
supporting information
p. 12724 - 12729
(2019/11/05)
-
- Synthesis of Diiodinated All-Carbon 3,3′-Diphenyl-1,1′-spirobiindene Derivatives via Cascade Enyne Cyclization and Electrophilic Aromatic Substitution
-
A synthetic method for the construction of diiodinated all-carbon spirobiindene derivatives has been developed from the reaction of propargyl alcohol-tethered alkylidenecyclopropanes with iodine. The reaction proceeded through an iodination-initiated cascade intramolecular enyne cyclization and electrophilic aromatic substitution reaction process in 1,2-dichloroethane upon heating, giving desired spirocyclic products in moderate to excellent yields. Further transformation of the obtained products has also been presented.
- Li, Quanzhe,Yu, Liuzhu,Wei, Yin,Shi, Min
-
p. 9282 - 9296
(2019/08/12)
-
- Palladium-Catalyzed Cascade Reductive and Carbonylative Cyclization of Ortho-Iodo-Tethered Methylenecyclopropanes (MCPs) Using N-Formylsaccharin as CO Source
-
A palladium-catalyzed reductive and carbonylative cyclization of ortho-iodo-tethered methylenecyclopropanes (MCPs) using N-formylsaccharin as CO source has been developed, affording the desired indanone derivatives in moderate to good yields with high regio- and stereoselectivity and good functional group compatibility.
- Fan, Xing,Shi, Min,Wei, Yin
-
p. 5677 - 5683
(2019/11/16)
-
- Enantioselective Intramolecular Copper-Catalyzed Borylacylation
-
An enantioselective copper-catalyzed intramolecular borylacylation is reported. The reaction proceeds through an initial enantioselective borylcupration of the styrene, followed by a nucleophilic attack on the tethered carbamoyl chloride. The products, chiral borylated 3,3-disubstituted oxindoles, were generated in excellent yields and enantioselectivities. The versatile carbon–boron bond provides a platform for a wide array of diversification.
- Whyte, Andrew,Burton, Katherine I.,Zhang, Jingli,Lautens, Mark
-
supporting information
p. 13927 - 13930
(2018/10/02)
-
- Chemoselective double annulation of two different isocyanides: Rapid access to trifluoromethylated indole-fused heterocycles
-
An unprecedented chemoselective double annulation of α-trifluoromethylated isocyanides with o-acylaryl isocyanides has been developed. This new reaction provides a rapid, efficient, and complete atom-economic strategy for the synthesis of trifluoromethylated oxadiazino[3,2-α]indoles in a single operation from readily available starting materials. Isocyanide insertion into C=O double bonds is disclosed for the first time as indicated by the results of 18O-labeling experiment. A mechanism for this domino reaction is proposed involving chemoselective heterodimerization of two different isocyanides, followed by indole-2,3-epoxide formation and rearrangement.
- Gao, Yuelei,Hu, Zhongyan,Dong, Jinhuan,Liu, Jun,Xu, Xianxiu
-
supporting information
p. 5292 - 5295
(2017/11/06)
-
- A mild and practical procedure for synthesis of substituted 2-aminobenzophenones
-
Abstract A convenient three-step procedure has been developed for synthesis of substituted 2-aminobenzophenones from substituted anilines. The anilines are first protected as acetanilides, by reaction with acetic anhydride. These are then benzoylated with (trichloromethyl)benzene in the presence of aluminium-generated 2-acetamidobenzophenone. Finally, removal of the acetyl group from the amino group provides the substituted 2-aminobenzophenones in moderate to good yields.
- Ma, Er-Qian,Wang, Ping,Li, Pei-He,Mo, Li-Ping
-
p. 6433 - 6441
(2015/08/18)
-
- Palladium-catalyzed direct addition of arylboronic acids to 2-aminobenzonitrile derivatives: Synthesis, biological evaluation and in silico analysis of 2-aminobenzophenones, 7-benzoyl-2-oxoindolines, and 7-benzoylindoles
-
A palladium-catalyzed direct addition of arylboronic acids to unprotected 2-aminobenzonitriles has been developed, leading to a wide range of 2-aminobenzophenones with moderate to excellent yields. The transformation has broad scope and high functional group tolerance. Moreover, 2-oxoindoline-7-carbonitrile and indole-7-carbonitrile were applicable to this process for the construction of 7-benzoyl-2-oxoindolines and 7-benzoylindoles, respectively. Among the compounds examined, compound 4e possessed the most potent anticancer activity against H446 and HGC-27 in vitro, with IC50 values of 0.02 μmol L-1 and 0.09 μmol L-1, respectively, while compound 4a showed the best potent anticancer activity against SGC-7901 with an IC50 value of 0.01 μmol L-1. Furthermore, we also performed in silico molecular docking calculations to investigate the interaction mode and binding affinity between the examined compounds and their tubulin target. This journal is
- Chen, Jiuxi,Ye, Leping,Su, Weike
-
supporting information
p. 8204 - 8211
(2015/01/08)
-
- Palladium-catalyzed direct addition of 2-Aminobenzonitriles to sodium arylsulfinates: Synthesis of o-Aminobenzophenones
-
The first example of the palladium-catalyzed synthesis of o-Aminobenzophenones in moderate to excellent yields via a direct addition of sodium arylsulfinates to unprotected 2-Aminobenzonitriles was reported. A plausible mechanism for the formation of o-Aminobenzophenones involving desulfination and addition reactions was proposed. The utility of this transformation was demonstrated by its compatibility with a wide range of functional groups. Thus, the method represents a convenient and practical strategy for synthesis of o-Aminobenzophenones.
- Chen, Jiuxi,Li, Jianjun,Su, Weike
-
p. 6439 - 6449
(2014/06/10)
-
- Ru(ii)-catalyzed intermolecular ortho-C-H amidation of aromatic ketones with sulfonyl azides
-
Ru(ii)-catalyzed intermolecular ortho-C-H amidation of weakly coordinating aromatic ketones with sulfonyl azides is reported. The developed reaction protocol can be extended to various substituted aromatic ketones to afford a wide range of desired C-N bond formation products in good yields.
- Bhanuchandra,Ramu Yadav,Rit, Raja K.,Rao Kuram, Malleswara,Sahoo, Akhila K.
-
supporting information
p. 5225 - 5227
(2013/06/27)
-
- Zinc Mediated Friedel-Crafts Acylation in Solvent-Free Conditions under Microwave Irradiation
-
Zn powder is found to catalyze the Friedel-Crafts acylation of aromatic compounds with acyl halides efficiently under microwave irradiation in solvent-free conditions. Activated substrates undergo acylation predominantly at the para-position. The Zn powder can be re-used up to six times after simple washing with diethyl ether and dilute HCl.
- Paul, Satya,Nanda, Puja,Gupta, Rajive,Loupy, Andre
-
p. 2877 - 2881
(2007/10/03)
-
- Synthesis and structure-activity relationship of 2-(aminoalkyl)-2,3,3a,8-tetrahydrodibenzo[c,f]isoxazolo[2,3-a]azepine derivatives: A novel series of 5-HT2A/2C receptor antagonists. Part 2
-
Following the programme started at Janssen Research Foundation searching for 5-HT2A/2C antagonists, we now report on the synthesis of a series of substituted 2-(Dimethylaminomethyl)-2,3,3a,8-tetrahydrodibenzo[c,f]isoxazolo[2,3-a] azepine derivatives. The 5-HT2A, 5-HT2C and H1 receptor affinities as well as the mCPP antagonistic activity of the compounds synthesised is described.
- Ignacio Andres,Alcazar, Jesus,Alonso, Jose M.,Diaz, Adolfo,Fernandez, Javier,Gil, Pilar,Iturrino, Laura,Matesanz, Encarna,Meert, Theo F.,Megens, Anton,Sipido, Victor K.
-
p. 249 - 253
(2007/10/03)
-
- Sandmeyer reactions. Part 5.1 Estimation of the rates of 1,5-aryl/aryl radical translocation and cyclisation during Pschorr fluorenone synthesis with a comparative analysis of reaction energetics
-
During the Pschorr cyclisation of 2-aroylphenyl radicals, a rearrangement occurs reversibly by 1,5-hydrogen transfer to give 2-benzoylaryl radicals. Rate constants of (1.2 ± 0.2) × 106 s-1 at 293 K are estimated for both the forward and back reactions in the equilibrium between 2-(4-methylbenzoyl)phenyl and 2-benzoyl-5-methylphenyl radicals. Assuming an empirical estimate of 1.6 × 10-2 dm3 mol-1 s-1 for the hypothetical rate of abstraction of hydrogen from benzene by phenyl radicals, the radical translocation is calculated to occur with a statistically corrected effective molarity of 2.2 × 108 mol dm-3. By contrast, the competing cyclisation, though occurring at a rate of (8.0 ± 0.9) × 105 s-1, exhibits an effective molarity of only 5.3 mol dm-3. The causes of these differences are analysed in terms of reaction mechanism.
- Chandler, Stephen A.
-
p. 214 - 228
(2007/10/03)
-
- Modification of Photochemical Reactivity by Cyclodextrin Complexation: Product Selectivity in Photo-Fries Rearrangement
-
Cyclodextrin encapsulation, both in the solid state and in aqueous solution brings about a remarkable regulation of the photo-Fries rearrangement of phenyl esters and anilides.In comparison to the non-selective mixture of ortho and para-rearranged isomers along with the deacylated product obtained in organic solvents, the solid β-cyclodextrin complexes of unsubstituted esters and anilides show a remarkable 'ortho-selectivity'.An impressive 'regio-selectivity' among the two ortho-rearranged isomers is observed for meta-substituted esters and anilides upon irradiation as β-cyclodextrin complexes.Specific orientations of the unsubstituted and meta-substituted esters and anilides in the β-cyclodextrin cavity are suggested to be responsible for the observed selectivity.
- Syamala, M. S.,Rao, B. Nageswer,Ramamurthy, V.
-
p. 7234 - 7242
(2007/10/02)
-