- Photo-induced oxidative cleavage of C-C double bonds of olefins in water
-
The carbonyl compounds, synthesized by the oxidative cleavage of their corresponding olefins, are of great significance in organic synthesis, especially aryl ketones. We have developed a gentle and effective protocol, using acid red 94 as the organic metal-free photocatalyst, O2 as the oxidant, and water as the solvent. Under visible light irradiation, aryl ketone derivatives were obtained in moderate to excellent yields, showing good economic and environmental advantages.
- Zhang, Yilan,Yue, Xiaoguang,Liang, Chenfeng,Zhao, Jianming,Yu, Wenbo,Zhang, Pengfei
-
supporting information
(2021/08/27)
-
- Selective oxidation of alkenes to carbonyls under mild conditions
-
Herein, a practical and sustainable method for the synthesis of aldehydes, ketones, and carboxylic acids from an inexpensive olefinic feedstock is described. This transformation features very sustainable and mild conditions and utilizes commercially available and inexpensive tetrahydrofuran as the additive, molecular oxygen as the sole oxidant and water as the solvent. A wide range of substituted alkenes were found to be compatible, providing the corresponding carbonyl compounds in moderate-to-good yields. The control experiments demonstrated that a radical mechanism is responsible for the oxidation reaction.
- Huo, Jie,Xiong, Daokai,Xu, Jun,Yue, Xiaoguang,Zhang, Pengfei,Zhang, Yilan
-
supporting information
p. 5549 - 5555
(2021/08/16)
-
- Aryl aldiketone and synthesis method thereof
-
The invention discloses an aryl aldehyde ketone and a synthesis method thereof, wherein an aryl aldehyde is synthesized from cheap olefin as a raw material. A commercially available inexpensive olefin is used as a raw material, ether is used as an additive, molecular oxygen serves as a sole oxidizing agent, water is used as a solvent, and the aldehyde and ketone are synthesized by column chromatography under a photocatalytic condition. The invention has the advantages of mild reaction conditions, green and environmental protection, simple experimental operation, good reaction selectivity, high product yield and the like.
- -
-
Paragraph 0030
(2021/09/26)
-
- AIBN initiated functionalization of the benzylic sp3 C[sbnd]H and C[sbnd]C bonds in the presence of dioxygen
-
A sp3 C[sbnd]H bond functionalization and C[sbnd]C bond cleavage were realized by AIBN/O2 catalyst system, providing a series of benzophenones under mild reaction conditions. The mechanistic study shows that a peroxide intermediate is involved in this transformation, and in the case of diphenylmethanes, the sp3 C[sbnd]C bond is cleaved through the peroxide rearrangement, which might provides a new way to cleave relatively strong C[sbnd]C bond and be applied to more general C[sbnd]C bond activation.
- Hu, Yingying,Shao, Yu,Zhang, Shuwei,Yuan, Yuan,Sun, Zheng,Yuan, Yu,Jia, Xiaodong
-
supporting information
(2021/02/01)
-
- Hydrogen-Bond-Donor Solvents Enable Catalyst-Free (Radio)-Halogenation and Deuteration of Organoborons
-
A hydrogen bond donor solvent assisted (radio)halogenation and deuteration of organoborons has been developed. The reactions exhibited high functional group tolerance and needed only an ambient atmosphere. Most importantly, compared to literature methods, our conditions are more consistent with the principals of green chemistry (e.g., metal-free, strong oxidant-free, more straightforward conditions).
- Yang, Yi,Gao, Xinyan,Zeng, Xiaojun,Han, Junbin,Xu, Bo
-
supporting information
p. 1297 - 1300
(2020/12/23)
-
- Chemoselective Synthesis of Aryl Ketones from Amides and Grignard Reagents via C(O)-N Bond Cleavage under Catalyst-Free Conditions
-
Conversion of a wide range of N-Boc amides to aryl ketones was achieved with Grignard reagents via chemoselective C(O)-N bond cleavage. The reactions proceeded under catalyst-free conditions with different aryl, alkyl, and alkynyl Grignard reagents. α-Ketoamide was successfully converted to aryl diketones, while α,β-unsaturated amide underwent 1,4-addition followed by C(O)-N bond cleavage to provide diaryl propiophenones. N-Boc amides displayed higher reactivity than Weinreb amides with Grignard reagents. A broad substrate scope, excellent yields, and quick conversion are important features of this methodology.
- Sureshbabu, Popuri,Azeez, Sadaf,Muniyappan, Nalluchamy,Sabiah, Shahulhameed,Kandasamy, Jeyakumar
-
p. 11823 - 11838
(2019/10/02)
-
- Connecting a carbonyl and a π-conjugated group through a: P-phenylene linker by (5+1) benzene ring formation
-
A benzene ring was formed to connect a carbonyl group of various methyl ketones with a π-conjugated group through a p-phenylene linker. Methyl ketones and streptocyanines were used as the C1 and C5 sources, respectively, in the (5+1) annulation, which could form donor-π-acceptor molecules.
- Morofuji, Tatsuya,Kinoshita, Hanae,Kano, Naokazu
-
supporting information
p. 8575 - 8578
(2019/07/25)
-
- Preparation method of aromatic ketone
-
The invention discloses a preparation method of aromatic ketone. Under the effects of a palladium catalyst and a nitrogen-containing ligand, nitrile compounds and arylsulfonylhydrazide take desulfurization addition reaction in an organic solvent; after the reaction is completed, post treatment is performed to obtain aromatic ketone. The reaction is applicable to aromatic nitrile compounds, and isalso applicable to aliphatic nitrile compounds; the reaction realizes the wide substrate applicability and functional group tolerance; the potential application value is realized in the aspect of aryl-carbonyl building.
- -
-
Paragraph 0046; 0047; 0048; 0050
(2018/09/11)
-
- Method for preparing aromatic ketone in aqueous phase
-
The invention discloses a method for preparing aromatic ketone in an aqueous phase, comprising the following steps: enabling aryl formyl potassium formate and aryl potassium fluoborate to generate decarboxylation acylation reaction in water under the actions of a silver catalyst and an oxidizing agent, and performing treatment after reaction is ended to obtain the disclosed aromatic ketone. According to the preparation method, the silver catalyst replaces a noble metal catalyst, water is taken as a solvent, an aromatic ketone product is obtained with relatively high yield, the adopted catalystis low in cost and easy to obtain, reaction conditions are mild, and meanwhile, the product is good in university, and therefore, the method has good application potential.
- -
-
Paragraph 0042-0045
(2018/04/26)
-
- Pd(II)-Catalyzed Denitrogenative and Desulfinative Addition of Arylsulfonyl Hydrazides with Nitriles
-
A Pd(II)-catalyzed denitrogenative and desulfinative addition of arylsulfonyl hydrazides with nitriles has been successfully achieved under mild conditions. This transformation is a new method for the addition reaction to nitriles with arylsulfonyl hydrazides as arylating agent, thus providing an alternative synthesis of aryl ketones. The reported addition reaction is tolerant to many common functional groups, and works well in the presence of electron-donating and electron-withdrawing substituents. Notably, the reported denitrogenative and desulfinative addition was also appropriate for alkyl nitriles, making this newly developed transformation attractive.
- Meng, Mengting,Yang, Liangfeng,Cheng, Kai,Qi, Chenze
-
p. 3275 - 3284
(2018/03/25)
-
- Carbonylative Suzuki Coupling Reaction Catalyzed by a Hydrospirophosphorane Palladium Complex
-
A Pd complex with the H-spirophosphorane ligand, PdCl2{P(OCMe2CMe2O)OC6H4NH2} (Cat. 1), was used as the catalyst in the carbonylative Suzuki coupling of substituted iodobenzenes with arylboronic acids and with sodium tetraphenylborate. Substituted diarylketones were obtained in good to excellent yields and a selectivity over 95 % under 1 atm of CO with 1.5 mol % of the catalyst. The promoting role of the H-spirophosphorane ligand in the catalytic process was evidenced. We used X-ray photoelectron spectroscopy, TEM, and 31P NMR spectroscopy to reveal that during the reaction Cat. 1 undergoes transformation into Pd complexes that bear the spirophosphorane ligand or other P ligands formed by its dealkylation and to Pd nanoparticles. All these Pd species contribute to the high productivity of the system.
- Wójcik, Przemys?aw,Sygellou, Labrini,Gniewek, Andrzej,Skar?yńska, Anna,Trzeciak, Anna
-
p. 4397 - 4409
(2017/11/21)
-
- Ag(i)/persulfate-catalyzed decarboxylative coupling of α-oxocarboxylates with organotrifluoroborates in water under room temperature
-
The decarboxylative coupling reaction of α-oxocarboxylates and organotrifluoroborates was carried out smoothly in the presence of catalytic AgNO3 using K2S2O8 as oxidant to generate diarylketone products in high
- Chang, Sheng,Wang, Jian Feng,Dong, Lin Lin,Wang, Dan,Feng, Bo,Shi, Yuan Tai
-
p. 51928 - 51934
(2017/11/22)
-
- Carbonylative Suzuki-Miyaura coupling catalyzed by palladium supported on aminopropyl polymethylsiloxane microspheres under atmospheric pressure of CO
-
Carbonylative Suzuki-Miyaura cross-coupling reactions of various aryl iodides with phenylboronic acids were catalyzed by palladium supported on amino-modified silica microspheres. Reactions performed with a very low concentration of Pd, under the atmospheric pressure of CO, led to high/moderate yields of multiple benzophenones.
- Zawartka, Wojciech,Po?piech, Piotr,Cypryk, Marek,Trzeciak, Anna M.
-
-
- Palladium catalyzed addition of arylboronic acid or indole to nitriles: Synthesis of aryl ketones
-
Aryl ketones can be synthesized conveniently by a palladium catalyzed addition of arylboronic acid to nitriles in aqueous triflic acid. This catalytic system was extended to the addition of unprotected indoles to nitriles under a slightly modified condition to produce 3-acyl indoles in good yields.
- Das, Tuluma,Chakraborty, Amarnath,Sarkar, Amitabha
-
supporting information
p. 7198 - 7202
(2015/01/09)
-
- Microwave-assisted facile and rapid friedel-crafts benzoylation of arenes catalyzed by bismuth trifluoromethanesulfonate
-
The catalytic activity of metal triflates was investigated in Friedel-Crafts benzoylation under microwave irradiation. Friedel-Crafts benzoylation with benzoyl chloride of a variety of arenes containing electron-rich and electron-poor rings using bismuth triflate under microwave irradiation is described. This method allows the preparation of aryl ketones under solventless conditions in good to excellent yields and short reaction time. Bismuth triflate was easily recovered and reused five times without significant loss of the catalytic activity.
- Tran, Phuong Hoang,Hansen, Poul Erik,Pham, Thuy Thanh,Huynh, Vy Thanh,Huynh, Vy Hieu,Thi Tran, Thao Du,Huynh, Thanh Van,Le, Thach Ngoc
-
p. 2921 - 2929
(2014/10/15)
-
- Copper-promoted reductive coupling of aryl iodides with 1,1,1-trifluoro-2-iodoethane
-
An efficient Cu-promoted reductive coupling of aryl iodides with 1,1,1-trifluoro-2-iodoethane has been developed. This reaction could occur in good yields under milder conditions as compared with previous studies. The reaction tolerated nitro, formyl, ester, ether, carbonyl, sulfonyl, and even azo groups.
- Xu, Song,Chen, Huan-Huan,Dai, Jian-Jun,Xu, Hua-Jian
-
supporting information
p. 2306 - 2309
(2014/05/20)
-
- Zinc-catalyzed benzylic C-H bond oxidation
-
A zinc-catalyzed oxidation of benzylic substrates has been developed. The corresponding carbonyl containing compounds have been produced in moderate to excellent yields. Both arenes and heteroarenes can be applied as substrates by using H2O2 as the oxidant.
- Wu, Xiao-Feng
-
p. 6123 - 6126
(2012/11/07)
-
- Cobalt-catalyzed preparation of arylindium reagents from aryl and heteroaryl bromides
-
A cobalt-bathophenanthroline catalyst has been developed for the direct preparation of a variety of arylindium reagents from the corresponding aryl and heteroaryl bromides in the presence of indium metal and lithium chloride. The thus-formed arylindium reagents undergo efficient palladium-catalyzed cross-coupling reactions with aryl iodides, tolerating various functional groups including hydroxy and free amino groups.
- Adak, Laksmikanta,Yoshikai, Naohiko
-
experimental part
p. 7563 - 7568
(2011/11/12)
-
- Designed synthesis of multi-electrochromic systems bearing diaryl ketone and isophthalates
-
New multi-electrochromic systems have been developed through the combination of a diaryl ketyl radical system with isophthalate-based electrochromic materials. The location of the isophthalate group in compounds is very critical to obtaining different colors in the multi-electrochromism.
- Sharmoukh,Ko, Kyoung Chul,Noh, Changho,Lee, Jin Yong,Son, Seung Uk
-
scheme or table
p. 6708 - 6711
(2010/12/19)
-
- A one-pot method for the iodination of aryl amines via stable aryl diazonium silica sulfates under solvent-free conditions
-
A convenient and rapid one-pot method for the synthesis of iodoarenes is developed which involves the sequential diazotization-iodination of aromatic amines with sodium nitrite, silica sulfuric acid and potassium iodide under solvent-free conditions at room temperature. Various aromatic amines possessing electron-withdrawing groups or electron-donating groups are converted into the corresponding aryl iodides in good yields. Georg Thieme Verlag Stuttgart.
- Zarei, Amin,Hajipour, Abdol R.,Khazdoozd, Leila
-
experimental part
p. 941 - 944
(2009/12/02)
-
- Ag-catalyzed stereoselective cyclohexadienyl transfer: A novel entry into arylphenylmethanols
-
The letter describes a novel concept for the synthesis of biologically important arylphenylmethanols. Stereoselective cyclohexadienyl transfer from 1,4-cyclohexadienyltributyltin to various aromatic aldehydes using AgOTf/BINAP as a catalyst precursor provides 1,4-cyclohexadienylphen-ylmethanols that are readily oxidized to the corresponding arylphenylmethanols. Fifteen examples are presented.
- Umeda, Rui,Studer, Armido
-
supporting information; experimental part
p. 993 - 996
(2009/04/07)
-
- Pd-P(t-Bu)3-catalyzed consecutive cross-coupling of p-phenylenedizinc compound with two different electrophiles leading to unsymmetrically 1,4-disubstituted benzenes
-
(Chemical Equation Presented) Pd-P(t-Bu)3 was found to be a chemoselective catalyst for the reaction of p-phenylenedizinc compound with equimolar amounts of carbon electrophiles to afford the single cross-coupling products in good yields, effectively suppressing the formation of double cross-coupling products. The subsequent additions of other electrophiles to the resulting solutions caused the second cross-coupling of the incipient products to take place, achieving a novel and efficient one-pot synthesis of unsymmetrically 1,4-disubstituted benzenes. The origin of the observed high chemoselectivity was speculated.
- Kawamoto, Takahiro,Ejiri, Shogo,Kobayashi, Kana,Odo, Shunsuke,Nishihara, Yasushi,Takagi, Kentaro
-
p. 1601 - 1604
(2008/09/17)
-
- Efficient one-pot transformation of aminoarenes to haloarenes using halodimethylisulfonium halides generated in situ
-
Halodimethylsulfonium halide 1, which is readily formed in situ from hydrohaloic acid and DMSO, is a good nucleophilic halide. This activated nucleophilic halide rapidly converts aryldiazonium salt prepared in situ by the same hydrohaloic acid and nitrite ion to aryl chlorides, bromides, or iodides in good yield. The combined action of nitrite ion and hydrohaloic acid in DMSO is required for the direct transformation of aromatic amines, which results in the production of aryl halides within 1 h. Substituted compounds with electron-donating or -withdrawing groups or sterically hindered aromatic amines are also smoothly transformed to the corresponding aromatic halides. The only observed by-product is the deaminated arene (usually 7%). The isolated aryldiazonium salts can also be converted to the corresponding aryl halides using 1. The present method offers a facile, one-step procedure for transforming aminoarenes to haloarenes and lacks the environmental pollutants that usually accompany the Sandmeyer reaction using copper halides.
- Baik, Woonphil,Luan, Wanqiang,Lee, Hyun Joo,Yoon, Cheol Hun,Koo, Sangho,Kim, Byeong Hyo
-
p. 213 - 219
(2007/10/03)
-
- N-chloro-3-methyl-2,6-diphenylpiperidin-4-one (NCP) - An efficient, mild, stable oxidant for cleavage of carbon-nitrogen double bonds of oximes
-
Aldoximes and ketoximes are effectively deoximated to regenerate the carbonyl compound by an efficient, mild, stable oxidant N-chloro-3-methyl-2,6-diphenylpiperidin-4-one (NCP).
- Balasubramanian,Ramalingan,Kabilan
-
p. 2979 - 2984
(2007/10/03)
-
- Application of a new kinetic method in the investigation of cleavage reactions of haloaromatic radical anions
-
A simple kinetic method based on competition kinetics is presented for the measurement of cleavage rate constants of radical anions over the range of 107 - 5 × 109 s-1 in aprotic solvents. The standard potential for the formation of the radical anions may be extracted from the kinetic analysis as well. The method employs electrochemical steady-state or optical detection techniques and is an extension of the redox catalysis approach described previously in the literature. The applicability of the method is illustrated through a systematic study of the cleavage reactions for a number of short-lived haloaromatic radical anions. Interestingly, the radical anion of iodobenzene is found to be an intermediate in the homogeneous reduction of iodobenzene, even though recent investigations have shown that the corresponding heterogeneous reduction at an electrode surface proceeds by a concerted electron transfer-bond cleavage process. The nature of the cleavage reactions is discussed in terms of the activation driving force plot of the cleavage rate constants versus the relevant Gibbs energies. While the exergonic cleavage reactions follow a simple decay mechanism taking place at the halogen site, the endergonic processes are best described as intra-molecular electron transfers from the substituent to the carbon-halogen bond. Nevertheless, the overall intrinsic barrier is found to be relatively small (27-39 kJ mol-1) and it is suggested that the endergonic reactions may proceed by a stepwise mechanism, in which a σ* radical anion is formed as an intermediate prior to the formation of the dissociated products, the aryl radical and the halide. The above conclusions were supported by semi-empirical PM3 calculations of structures and charge distributions in the radical anions.
- Enemaerke, Rasmus J.,Christensen, Torben B.,Jensen, Henrik,Daasbjerg, Kim
-
p. 1620 - 1630
(2007/10/03)
-
- Photoinduced Radical Cleavage of Iodobenzophenones
-
The triplet state cleavage of m-iodo-(mibp) and p-iodobenzophenone (pIBP) to benzoylphenyl and iodine radicals has been studied by both steady state and laser flash techniques.Phosphorescence spectra in methanol/ ethanol glasses at 77 K indicate triplet energies of 68.4 and 67.8 kcal/mol for mIBP and pIBP, respectively.In most organic solvents products are benzophenone and iodinated solvents; these are formed by hydrogen abstraction from solvent by the initially formed benzoylphenyl radicals.Quantum yields for product formation decrease with increasing solvent viscosity, ranging from 0.45 in acetonitrile to 0.28 in cyclopentane and 0.05 in cyclooctane; they appear to reflect significant in-cage recoupling of the initial radical pairs.Quenching of the reaction by naphthalene indicates 25 degC triplet lifetimes of 25 and 0.2 ns for mIBP and pIBP, respectively, which were confirmed by flash kinetics.Laser excitation produced transient signals assigned to the iodine atom-toluene complex (in toluene) and, for mIBP, the triplet ketone.Decay of the latter revealed activation parameters ΔH = 4.0 +/- 0.2 kcal/mol and log A = 10.6 +/- 0.2 for mIBP in both methanol and toluene.The strong phosphorescence of both ketones at 77 K indicates that ΔH for pIBP must be >= 3kcal/mol, such that log A is ca. 12, much higher than for mIBP.The different rates and A values reflect different ?* spin densities at the meta and para positions in the lowest n,?* triplets, which react either by mixing with dissociative ?,?* states or by thermally converting into a dissociative ?,?* or ?1,?* state.The dependence of ?* spin density and the low A values strongly suggest an inefficient state interconversion at a surface crossing between n,?* and ?,?* states, because of their different symmetries.It is suggested that the low A values, which might indicate negative Δs values, are better understood as low transmission coefficients.
- Wagner, Peter J.,Waite, Carol I.
-
p. 7388 - 7394
(2007/10/02)
-
- The Decomposition of Arenediazonium Tetrafluoroborates with Halo- and Azidotrimethylsilanes in Nonaqueous Solvents
-
The reaction of arenediazonium tetrafluoroborates with chlorotrimethylsilane in a tetrahydrofuran/N,N-dimethylformamide (DMF) (5v/3v) solution afforded the protodediazotization products in high yields.The reactions of the diazonium salts with halotrimethylsilanes in DMF were found to give the corresponding haloarenes.Among the halodediazotization reactions, the iododediazotization with iodotrimethylsilane proceeded smoothly at room temperature to give the iodoarenes in excellent yields.In a similar manner, a variety of azidoarenes were obtained in cosistently high yields by the treatment of arenediazonium tetrafluoroborates with azidotrimethylsilane in a DMF solution.
- Keumi, Takashi,Umeda, Toshiaki,Inoue, Yoshinori,Kitajima, Hidehiko
-
-
- Synthesis of Some Substituted Dimethyl and Diethyl 4-(Phenylethynyl)-2,6-pyridinedicarboxylates
-
Substituted dimethyl and diethyl 4-(phenylethynyl)-2,6-pyridinedicarboxylates were prepared by coupling reactions between dialkyl 4-halo-2,6-pyridinedicarboxylates and terminal arylacetylenes in the presence of an organopalladium catalyst and copper(I) iodide in a suitable solvent system.The terminal acetylenes needed in this work were synthesized from the corresponding aryl halides using either (trimethylsilyl)acetylene or 2-methyl-3-butyn-2-ol followed by deprotection of the triple bond, depending on the nature of the compound in question.
- Takalo, Harri,Kankare, Jouko,Haenninen, Elina
-
p. 448 - 454
(2007/10/02)
-
- Reaction of Diazonium Salts with Transition Metals. Part 13. Palladium-catalyzed Carbonylative Coupling of Arenediazonium Salts with Organotin Reagents to give Aromatic Ketones
-
Palladium-catalyzed reactions of arenediazonium salts (ArN2X; Ar=Y-Ph, Y=H, 2-, 3-, 4-Me, 2-Ph, 2-, 3-MeO, 2-, 3-, 4-Cl, 4-Br, 4-I, 2-, 3-, and 4-NO2, X=BF4 and PF6) with carbon monoxide and organostannanes (R4Sn, R=Me, Et, and Ph; RSnMe3, R=Ph, 2-, 3-, 4-MeC6H4, and 4-ClC6H4; RSnEt3, R=4-NO2C6H4; RSnBu3, R=Ph) gave aromatic ketones (ArCOR) in good yields (40-95percent) at room temperature.
- Kikukawa, Kiyoshi,Idemoto, Tohru,Katayama, Atsuhiko,Kono, Kiyoshi,Wada, Fumio,Matsuda, Tsutomu
-
p. 1511 - 1514
(2007/10/02)
-