cas 3457-45-2, 4-ACETYLBENZALDEHYDE | Articles data

Articles about 3457-45-2Total 90 be found

Article title
Article abstract
Author
Journal number and time
Download

Simultaneous functional group manipulation in the Meerwein-Ponndorf- Verley reduction process catalyzed by bidentate aluminum reagent
Simultaneous reduction/oxidation sequence of hydroxy carbonyl substrates through Meerwein-Ponndorf-Verley reduction can be facilitated in the presence of bidentate aluminum catalyst, (2,7-dimethyl-1,8- biphenylenedioxy)bis(dimethylaluminum). This new appr
Ooi, Takashi,Itagaki, Yoshifumi,Miura, Tomoya,Maruoka, Keiji
p. 2137 - 2138
(1999)
Read Online

Iron(III) Nitrate/TEMPO-Catalyzed Aerobic Alcohol Oxidation: Distinguishing between Serial versus Integrated Redox Cooperativity
Aerobic alcohol oxidations catalyzed by transition metal salts and aminoxyls are prominent examples of cooperative catalysis. Cu/aminoxyl catalysts have been studied previously and feature "integrated cooperativity", in which CuII and the aminoxyl participate together to mediate alcohol oxidation. Here we investigate a complementary Fe/aminoxyl catalyst system and provide evidence for "serial cooperativity", involving a redox cascade wherein the alcohol is oxidized by an in situ-generated oxoammonium species, which is directly detected in the catalytic reaction mixture by cyclic step chronoamperometry. The mechanistic difference between the Cu- and Fe-based catalysts arises from the use iron(III) nitrate, which initiates a NOx-based redox cycle for oxidation of aminoxyl/hydroxylamine to oxoammonium. The different mechanisms for the Cu- and Fe-based catalyst systems are manifested in different alcohol oxidation chemoselectivity and functional group compatibility.
Mao, Kaining,Nutting, Jordan E.,Stahl, Shannon S.
supporting information
p. 10565 - 10570
(2021/07/28)

Merging N-Hydroxyphthalimide into Metal-Organic Frameworks for Highly Efficient and Environmentally Benign Aerobic Oxidation
Two highly efficient metal-organic framework catalysts TJU-68-NHPI and TJU-68-NDHPI have been successfully synthesized through solvothermal reactions of which the frameworks are merged with N-hydroxyphthalimide (NHPI) units, resulting in the decoration of pore surfaces with highly active nitroxyl catalytic sites. When t-butyl nitrite (TBN) is used as co-catalyst, the as-synthesized MOFs are demonstrated to be highly efficient and recyclable catalysts for a novel three-phase heterogeneous oxidation of activated C?H bond of primary and secondary alcohols, and benzyl compounds under mild conditions. Based on the high efficiency and selectivity, an environmentally benign system with good sustainability, mild conditions, simple work-up procedure has been established for practical oxidation of a wide range of substrates.
Wang, Man,Liang, Gan,Wang, Yunhao,Fan, Tao,Yuan, Baoling,Liu, Mingxian,Yin, Ying,Li, Liangchun
supporting information
p. 9674 - 9685
(2021/06/09)

Catalytic Aerobic Oxidation of Alkenes with Ferric Boroperoxo Porphyrin Complex; Reduction of Oxygen by Iron Porphyrin
We herein describe the development of a mild and selective catalytic aerobic oxidation process of olefins. This catalytic aerobic oxidation reaction was designed based on experimental and spectroscopic evidence assessing the reduction of atmospheric oxygen using a ferric porphyrin complex and pinacolborane to form a ferric boroperoxo porphyrin complex as an oxidizing species. The ferric boroperoxo porphyrin complex can be utilized as an in-situ generated intermediate in the catalytic aerobic oxidation of alkenes under ambient conditions to form oxidation products that differ from those obtained using previously reported ferric porphyrin catalysis. Moreover, the mild reaction conditions allow chemoselective oxidation to be achieved.
Kimura, Kento,Kurahashi, Takuya,Matsubara, Seijiro,Murano, Shunpei
supporting information
p. 2493 - 2497
(2021/12/29)

Iron-catalyzed domino decarboxylation-oxidation of α,β-unsaturated carboxylic acids enabled aldehyde C-H methylation
A practical and general iron-catalyzed domino decarboxylation-oxidation of α,β-unsaturated carboxylic acids enabling aldehyde C-H methylation for the synthesis of methyl ketones has been developed. This mild, operationally simple method uses ambient air as the sole oxidant and tolerates sensitive functional groups for the late-stage functionalization of complex natural-product-derived and polyfunctionalized molecules.
Gong, Pei-Xue,Xu, Fangning,Cheng, Lu,Gong, Xu,Zhang, Jie,Gu, Wei-Jin,Han, Wei
supporting information
p. 5905 - 5908
(2021/06/18)

Palladium-Catalyzed Reductive Carbonylation of (Hetero) Aryl Halides and Triflates Using Cobalt Carbonyl as CO Source
An efficient protocol for the reductive carbonylation of (hetero) aryl halides and triflates under CO gas-free conditions using Pd/Co2(CO)8 and triethylsilane has been developed. The mild reaction conditions, enhanced chemoselectivity and, easy access to heterocyclic and vinyl carboxaldehydes highlights its importance in organic synthesis.
Dogga, Bhushanarao,Joseph, Jayan T.,Kumar, C. S. Ananda
supporting information
p. 309 - 313
(2020/12/23)

A Magnetically Recyclable Palladium-Catalyzed Formylation of Aryl Iodides with Formic Acid as CO Source: A Practical Access to Aromatic Aldehydes
A magnetically recyclable palladium-catalyzed formylation of aryl iodides under CO gas-free conditions has been developed by using a bidentate phosphine ligand-modified magnetic nanoparticles-anchored- palladium(II) complex [2P-Fe 3O 4@SiO 2-Pd(OAc) 2] as catalyst, yielding a wide variety of aromatic aldehydes in moderate to excellent yields. Here, formic acid was employed as both the CO source and the hydrogen donor with iodine and PPh 3as the activators. This immobilized palladium catalyst can be obtained via a simple preparative procedure and can be facilely recovered simply by using an external magnetic field, and reused at least 9 times without any apparent loss of catalytic activity.
You, Shengyong,Zhang, Rongli,Cai, Mingzhong
p. 1962 - 1970
(2021/01/25)

Metal- And additive-free C-H oxygenation of alkylarenes by visible-light photoredox catalysis
A metal- and additive-free methodology for the highly selective, photocatalyzed C-H oxygenation of alkylarenes under air to the corresponding carbonyls is presented. The process is catalyzed by an imide-acridinium that forms an extremely strong photooxidant upon visible light irradiation, which is able to activate inert alkylarenes such as toluene. Hence, this is an easy to perform, sustainable and environmentally friendly oxidation that provides valuable carbonyls from abundant, readily available compounds.
García Manche?o, Olga,Kuhlmann, Jan H.,Pérez-Aguilar, María Carmen,Piekarski, Dariusz G.,Uygur, Mustafa
supporting information
p. 3392 - 3399
(2021/05/21)

Decarboxylative formylation of aryl halides with glyoxylic acid by palladium catalysis under oxygen
A new free radical/palladium cooperative catalyzed formylation of aryl halides with glyoxylic acid as the formyl source under oxygen conditions has been developed. Various aromatic and heteroaromatic aldehydes were produced in medium to good yields.
Cao, Hualiang,Pu, Weiwen,Zhang, Jie,Yan, Peijun,Zhang, Jun,Xu, Sheng
supporting information
p. 1287 - 1290
(2020/08/21)

Visible-light-promoted site-specific and diverse functionalization of a c(sp3)-c(sp3) bond adjacent to an arene
We report here a strategy for inert C-C bond functionalization. Site-specific cleavage and functionalization of a saturated C(sp3)-C(sp3) bond via a visible-light-induced radical process have been achieved. The general features of this reaction are as follows. (1) Both linear and cyclic C(sp3)-C(sp3) bonds with a vicinal arene can be specifically functionalized. (2) One carbon is converted into a ketone, and another can be tunably converted into nitrile, peroxide, or halide. (3) The typical conditions include 1.0 mol % of Ru(bpy)3Cl2, 1.0 or 5.0 equiv of Zhdankin reagent, white CFL (24 W), open flask, and room temperature. These reactions offer powerful tools to modify carbon skeletons that are intractable by conventional methods. Good selectivity and functional group tolerance, together with mild and open air conditions, make these transformations valuable and attractive.
Fang, Fang,Liu, Zhong-Quan,Sun, Minzhi,Wang, Nengyong,Wang, Yaxin,You, Huichao,Zhao, Jianyou
p. 6603 - 6612
(2020/07/27)

Continuous flow synthesis of aryl aldehydes by Pd-catalyzed formylation of phenol-derived aryl fluorosulfonates using syngas
This communication describes the palladium-catalyzed reductive carbonylation of aryl fluorosulfonates (ArOSO2F) using syngas as an inexpensive and sustainable source of carbon monoxide and hydrogen. The conversion of phenols to aryl fluorosulfonates can be conveniently achieved by employing the inexpensive commodity chemical sulfuryl fluoride (SO2F2) and base. The developed continuous flow formylation protocol requires relatively low loadings for palladium acetate (1.25 mol%) and ligand (2.5 mol%). Good to excellent yields of aryl aldehydes were obtained within 45 min for substrates containing electron withdrawing substituents, and 2 h for substrates containing electron donating substituents. The optimal reaction conditions were identified as 120 °C temperature and 20 bar pressure in dimethyl sulfoxide (DMSO) as solvent. DMSO was crucial in suppressing Pd black formation and enhancing reaction rate and selectivity. This journal is
Hanselmann, Paul,Hone, Christopher A.,Hu, Guixian,K?ckinger, Manuel,Kappe, C. Oliver
p. 22449 - 22453
(2020/07/03)

Rhodium-catalyzed reductive carbonylation of aryl iodides to arylaldehydes with syngas
The reductive carbonylation of aryl iodides to aryl aldehydes possesses broad application prospects. We present an efficient and facile Rh-based catalytic system composed of the commercially available Rh salt RhCl3·3H2O, PPh3 as phosphine ligand, and Et3N as the base, for the synthesis of arylaldehydes via the reductive carbonylation of aryl iodides with CO and H2 under relatively mild conditions with a broad substrate range affording the products in good to excellent yields. Systematic investigations were carried out to study the experimental parameters. We explored the optimal ratio of Rh salt and PPh3 ligand, substrate scope, carbonyl source and hydrogen source, and the reaction mechanism. Particularly, a scaled-up experiment indicated that the catalytic method could find valuable applications in industrial productions. The low gas pressure, cheap ligand and low metal dosage could significantly improve the practicability in both chemical researches and industrial applications.
Chen, Suqing,Liu, Zhenghui,Mu, Tiancheng,Wang, Peng,Yan, Zhenzhong,Yu, Dongkun,Zhao, Xinhui
p. 645 - 656
(2020/05/14)

Continuous-flow Synthesis of Aryl Aldehydes by Pd-catalyzed Formylation of Aryl Bromides Using Carbon Monoxide and Hydrogen
A continuous-flow protocol utilizing syngas (CO and H2) was developed for the palladium-catalyzed reductive carbonylation of (hetero)aryl bromides to their corresponding (hetero)aryl aldehydes. The optimization of temperature, pressure, catalyst and ligand loading, and residence time resulted in process-intensified flow conditions for the transformation. In addition, a key benefit of investigating the reaction in flow is the ability to precisely control the CO-to-H2 stoichiometric ratio, which was identified as having a critical influence on yield. The protocol proceeds with low catalyst and ligand loadings: palladium acetate (1 mol % or below) and cataCXium A (3 mol % or below). A variety of (hetero)aryl bromides at a 3 mmol scale were converted to their corresponding (hetero)aryl aldehydes at 12 bar pressure (CO/H2=1:3) and 120 °C reaction temperature within 45 min residence time to afford products mostly in good-to-excellent yields (17 examples). In particular, a successful scale-up was achieved over 415 min operation time for the reductive carbonylation of 2-bromo-6-methoxynaphthalene to synthesize 3.8 g of 6-methoxy-2-naphthaldehyde in 85 % isolated yield. Studies were conducted to understand catalyst decomposition within the reactor by using inductively coupled plasma–mass spectrometry (ICP–MS) analysis. The palladium could easily be recovered using an aqueous nitric acid wash post reaction. Mechanistic aspects and the scope of the transformation are discussed.
Hone, Christopher A.,Lopatka, Pavol,Munday, Rachel,O'Kearney-McMullan, Anne,Kappe, C. Oliver
p. 326 - 337
(2018/11/23)

Chemoselective reduction of aldehydes: Via a combination of NaBH4 and acetylacetone
A bench-stable combination of NaBH4-acetylacetone was developed for the efficient chemoselective reduction of aldehydes in the presence of ketones. This method offers a useful synthetic protocol for distinguishing carbonyl reaction sites, and its synthetic utility is reflected by its moisture tolerance and high efficiency in a variety of complex settings.
Sui, Guoqing,Lv, Qingyun,Song, Xiaoqing,Guo, Huihui,Dai, Jiatong,Ren, Li,Lee, Chi-Sing,Zhou, Wenming,Hao, Hong-Dong
p. 15793 - 15796
(2019/10/19)

PdO nanoparticles supported on triazole functionalized porous triazine polymer as an efficient heterogeneous catalyst for carbonylation of aryl halides
A well-defined triazole functionalized porous triazine based polymers act as solid heterogeneous catalyst after incorporating palladium oxide nanoparticles (PdO@TTAS) have been synthesized and thoroughly characterized by various techniques such as, FT-IR, UV-DRS, solid state 13C CP-MAS, XPS, powder X-ray diffraction, TGA, SEM and TEM analysis has been detailed illustrated. It is important to note that synthesized catalytic performance for carbonylation of aryl halides (X?=?I, Br) with EDC.HCl (N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride), and formic acid was found to be an effective CO source in the presence of triethylamine as a base and DMF as a solvent medium at 80?°C for about 3?hr. The PdO@TTAS catalyst exhibits superior catalytic performance and along with good yield (up to 90%). Moreover, studying the heterogeneity and reusability of the environmentally friendly solid catalyst can be easily separated by simple filtration and then recycled for several times. In this reaction method, we avoided ligand, additive, promoters and CO gas, due to additional problem arise by using gaseous CO, highly toxic greenhouse gases and high pressurized reaction setup.
Sadhasivam, Velu,Balasaravanan, Rajendran,Siva, Ayyanar
supporting information

(2019/07/03)

Cobalt(ii)-catalyzed benzylic oxidations with potassium persulfate in TFA/TFAA
A cobalt-catalyzed C(sp3)-H oxygenation reaction to furnish aldehyde was herein reported. This transformation demonstrated high chemo-selectivity, and tolerated various methylarenes bearing electron-withdrawing substituents. This reaction provided rapid access to diverse aldehydes form methylarenes. Notably, TFA/TFAA was used for the first time as a mixed solvent in cobalt-catalyzed oxygenation of benzylic methylenes.
Li, Tianlei,Li, Jishun,Zhu, Zihao,Pan, Weidong,Wu, Song
p. 20879 - 20883
(2019/07/12)

Nickel-Catalyzed Selective Reduction of Carboxylic Acids to Aldehydes
The direct reduction of carboxylic acids to aldehydes is a fundamental transformation in organic synthesis. The combination of an air-stable Ni precatalyst, dimethyl dicarbonate as an activator, and silane reductant effects this reduction for a wide variety of substrates, including pharmaceutically relevant structures, in good yields and with no overreduction to alcohols. Moreover, this methodology is scalable, allows access to deuterated aldehydes, and is also compatible with one-pot utilization of the aldehyde products.
Iosub, Andrei V.,Morav?ík, ?tefan,Wallentin, Carl-Johan,Bergman, Joakim
supporting information
p. 7804 - 7808
(2019/10/14)

Studies on Iron-Catalyzed Aerobic Oxidation of Benzylic Alcohols to Carboxylic Acids
A comprehensive study on aerobic oxidation of benzylic alcohols to carboxylic acids with a catalytic amount each of Fe(NO 3) 3 ·9H 2 O, TEMPO, and KCl is conducted. Various synthetically useful functional groups are well tolerated in the reaction. Distinct electronic and steric effects are observed in the reaction: electron-withdrawing groups accelerate the reaction while electron-donating groups make the reaction slower, and ortho -substituted substrates react slower than meta -substituted substrates. Several large-scale reactions (100 mmol) are conducted using a slow air flow of 30 mL/min to demonstrate the practicality of this method in an academic laboratory.
Jiang, Xingguo,Ma, Shengming
p. 1629 - 1639
(2018/02/26)

Dichlorophenobarbital: An efficient and selective reagent for deoximation of oximes to the carbonyl compounds
A simple, fast and efficient procedure for the cleavage of a wide of range ketoximes and al-doximes to the corresponding compounds using a safe and low-cost reagent, N,N′-dichlorophenobarbital, under mild reaction conditions at room temperature is described.
Shiri, Azam,Khoramabadi-Zad, Ahmad,Esmaili-Nezhad, Fateme
p. 833 - 837
(2018/11/06)

Rhodium-Catalyzed Formylation of Aryl Halides with CO2 and H2
The reductive formylation of aryl iodides/bromides to aryl aldehydes using CO2/H2 is presented for the first time. It was realized over a catalytic system composed of RhI3 or RhI3/Pd(dppp)Cl2 (dppp = 1,3-bis(diphenyphosphino)propane) and PPh3 in the presence of Ac2O/Et3N at 100 °C, affording aromatic aldehydes in good to excellent yields, together with good functional-group tolerance and broad substrate scope. The reaction proceeds through three cascade steps, involving HCOOH formation, CO release, and formylation of aryl halides.
Liu, Zhenghui,Yang, Zhenzhen,Yu, Bo,Yu, Xiaoxiao,Zhang, Hongye,Zhao, Yanfei,Yang, Peng,Liu, Zhimin
supporting information
p. 5130 - 5134
(2018/09/13)

Chemoselective Reduction of Sterically Demanding N,N-Diisopropylamides to Aldehydes
A sequential one-pot process for chemoselectively reducing sterically demanding N,N-diisopropylamides to aldehydes has been developed. In this reaction, amides are activated with EtOTf to form imidates, which are reduced with LiAlH(OR)3 [R = t-Bu, Et] to give aldehydes by hydrolysis of the resulting hemiaminals. The non-nucleophilic base 2,6-DTBMP remarkably improves reaction efficiency. The combination of EtOTf/2,6-DTBMP and LiAlH(O-t-Bu)3 was found to be optimal for reducing alkyl, alkenyl, alkynyl, and 2-monosubstituted aryl N,N-diisopropylamides. In contrast, EtOTf and LiAlH(OEt)3 in the absence of base were found to be optimal for reducing extremely sterically demanding 2,6-disubstituted N,N-diisopropylbenzamides. The reaction tolerates various reducible functional groups, including aldehyde and ketone. 1H NMR studies confirmed the formation of imidates stable in water. The synthetic usefulness of this methodology was demonstrated with N,N-diisopropylamide-directed ortho-metalation and C-H bond activation.
Xiao, Peihong,Tang, Zhixing,Wang, Kai,Chen, Hua,Guo, Qianyou,Chu, Yang,Gao, Lu,Song, Zhenlei
p. 1687 - 1700
(2018/02/23)

Generation of Phosphoranyl Radicals via Photoredox Catalysis Enables Voltage-Independent Activation of Strong C-O Bonds
Despite the prevalence of alcohols and carboxylic acids as functional groups in organic molecules and the potential to serve as radical precursors, C-O bonds remain difficult to activate. We report a synthetic strategy for direct access to both alkyl and acyl radicals from these ubiquitous functional groups via photoredox catalysis. This method exploits the unique reactivity of phosphoranyl radicals, generated from a polar/SET crossover between a phosphine radical cation and an oxygen-centered nucleophile. We show the desired reactivity in the reduction of benzylic alcohols to the corresponding benzyl radicals with terminal H atom trapping to afford the deoxygenated products. Using the same method, we demonstrate access to synthetically versatile acyl radicals, which enables the reduction of aromatic and aliphatic carboxylic acids to the corresponding aldehydes with exceptional chemoselectivity. This protocol also transforms carboxylic acids to heterocycles and cyclic ketones via intramolecular acyl radical cyclizations to forge C-O, C-N, and C-C bonds in a single step.
Stache, Erin E.,Ertel, Alyssa B.,Rovis, Tomislav,Doyle, Abigail G.
p. 11134 - 11139
(2018/11/21)

Oxidation of alkanes and secondary alcohols to ketones with tert-butyl hydroperoxide catalyzed by a water-soluble ruthenium complex under solvent-free conditions
An easily synthesized water-soluble ruthenium complex, [C6H5CH2N(CH3)2H]2[Ru(dipic)Cl3] (dipic =2,6-pyridinedicarboxylate), as a catalyst showed high efficiency in the oxidation of alkanes and secondary alcohols to their corresponding ketones under solvent-free and low-catalyst-loading conditions. This catalytic system could tolerate a variety of substrates and gave the corresponding ketones in good to excellent yields. The products were easily separated and purified due to the water solubility of the ruthenium complex.
Zhang, Yuecheng,Zhao, Liyuan,Zhang, Hongyu,Huang, Rong,Zhao, Jiquan
(2017/09/01)

Metal- and O2-Free Oxidative C-C Bond Cleavage of Aromatic Aldehydes
An oxidative C-C cleavage of aldehydes requiring neither metals nor O2 was discovered. Homobenzylic aldehydes and α-substituted homobenzylic aldehydes were cleaved to benzylic aldehydes and ketones, respectively, using nitrosobenzene as an oxidant. This reaction is chemoselective for aromatic aldehydes, as an aliphatic aldehyde was unreactive under these conditions, and other reactive functionality such as ketones and free alcohols are tolerated. A mechanism accounting for the fate of the lost carbon is proposed.
Hu, Guang,Ramakumar, Kinthada,Brenner-Moyer, Stacey E.
p. 6972 - 6977
(2017/07/17)

Visible-Light-Promoted Nickel- and Organic-Dye-Cocatalyzed Formylation Reaction of Aryl Halides and Triflates and Vinyl Bromides with Diethoxyacetic Acid as a Formyl Equivalent
A simple formylation reaction of aryl halides, aryl triflates, and vinyl bromides under synergistic nickel- and organic-dye-mediated photoredox catalysis is reported. Distinct from widely used palladium-catalyzed formylation processes, this reaction proceeds by a two-step mechanistic sequence involving initial in situ generation of the diethoxymethyl radical from diethoxyacetic acid by a 4CzIPN-mediated photoredox reaction. The formyl-radical equivalent then undergoes nickel-catalyzed substitution reactions with aryl halides and triflates and vinyl bromides to form the corresponding aldehyde products. Significantly, besides aryl bromides, less reactive aryl chlorides and triflates and vinyl halides serve as effective substrates for this process. Since the mild conditions involved in this reaction tolerate a plethora of functional groups, the process can be applied to the efficient preparation of diverse aromatic aldehydes.
Huang, He,Li, Xiangmin,Yu, Chenguang,Zhang, Yueteng,Mariano, Patrick S.,Wang, Wei
supporting information
p. 1500 - 1505
(2017/02/05)

Palladium-Catalyzed Ligand-Controlled Selective Synthesis of Aldehydes and Acids from Aryl Halides and Formic Acid
Selective synthesis is in the core of modern organic chemistry. In this communication, a novel ligand-dependent palladium-catalyzed carbonylation procedure for the divergent synthesis of aldehydes and carboxylic acids from easily available aryl halides was established. Under the same reaction conditions, the reaction pathway could be controlled by the ligands applied to give formylated and carboxylated products selectively. Sterically hindered monodentate ligands facilitated the reductive carbonylation and provided aldehydes, whereas bidentate ligands preferred the carboxylation reaction and produced carboxylic acids. A wide range of functional groups were tolerated, and the products were, in general, obtained in moderate to excellent yields.
Wu, Fu-Peng,Peng, Jin-Bao,Meng, Ling-Shen,Qi, Xinxin,Wu, Xiao-Feng
p. 3121 - 3124
(2017/08/29)

Selective Aerobic Oxidation of Methylarenes to Benzaldehydes Catalyzed by N-Hydroxyphthalimide and Cobalt(II) Acetate in Hexafluoropropan-2-ol
Efficient and highly selective catalytic conditions for the aerobic autoxidation of methylarenes to benzaldehydes, based on N-hydroxyphthalimide (NHPI) and cobalt(II) acetate in 1,1,1,3,3,3-hexafluoropropan-2-ol (HFIP), were developed. The sustainable conditions enable a multigram scale preparation of benzaldehyde derivatives in high efficiency and with excellent chemoselectivity (up to 99 % conversion and 98 % selectivity).
Gaster, Eden,Kozuch, Sebastian,Pappo, Doron
supporting information
p. 5912 - 5915
(2017/05/12)

BTK INHIBITOR
Provided are a series of BTK inhibitors, and specifically disclosed are a compound, pharmaceutically acceptable salt thereof, tautomer thereof or prodrug thereof represented by formula (I), (II), (III) or (IV).
-
(2017/11/16)

Novel oxidative aromatic alkene cleavage with sodium nitrite under mild conditions
We have developed a simple and practical process for the oxidation of aromatic alkene to the corresponding carbonyl compounds using NaNO2 as an oxidant. The practical utility of this oxidative process has been demonstrated in the gram-scale oxidation of 1-(tert-butyl)-4-vinylbenzene.
Yin, Bo,Peng, Xiangjun,Huang, Panpan,Huang, Qing,Liu, Liangxian
supporting information
p. 2189 - 2194
(2017/11/15)

Method of manufacturing calbonyl compd.
PROBLEM TO BE SOLVED: To provide a method of manufacturing a carbonyl compound by smoothly performing a dehydrogenation reaction while preventing side reactions.SOLUTION: A method of manufacturing a carbonyl compound includes a process of converting alcohol to aldehyde or ketone by irradiating visible light to a reaction system containing a primary alcohol or a secondary alcohol, SrTiOcarrying a Ru atom and doped with Rh atom, and water.
-
Paragraph 0028-0052

(2018/06/30)

A Convenient Palladium-Catalyzed Reductive Carbonylation of Aryl Iodides with Dual Role of Formic Acid
Palladium-catalyzed reductive carbonylation of aryl halides represents a straightforward pathway for the synthesis of aromatic aldehydes. The known reductive carbonylation procedures either require CO gas or complexed compounds as CO sources. In this communication, we developed a palladium-catalyzed reductive carbonylation of aryl iodides with formic acid as the formyl source. As a convenient, practical, and environmental friendly methodology, no additional silane or H2 was required. A variety of aromatic aldehydes were isolated in moderate to excellent yields under mild reaction conditions. Notably, this is the first procedure on using formic acid as the formyl source. Say no to CO gas! A convenient, practical, and environmental friendly palladium-catalyzed reductive carbonylation of aryl iodides with formic acid as the formyl source has been developed (see scheme). No additional silane or H2 was required here. A variety of aromatic aldehydes were isolated in moderate to excellent yields under mild reaction conditions.
Qi, Xinxin,Li, Chong-Liang,Wu, Xiao-Feng
supporting information
p. 5835 - 5838
(2016/04/26)

Palladium-catalyzed synthesis of aldehydes from aryl halides and tert-butyl isocyanide using formate salts as hydride donors
An efficient one-pot palladium-catalyzed hydroformylation of aryl halides to produce aromatic aldehydes has been achieved, employing tert-butyl isocyanide as a C1 resource and formate salt as a hydride donor without any additional bases. Characterized by its mild reaction conditions, easy operation and lower toxicity, this reaction can tolerate a wide array of functional groups with moderate to excellent yields.
Zhang, Ying,Jiang, Xiao,Wang, Jin-Mei,Chen, Jing-Lei,Zhu, Yong-Ming
p. 17060 - 17063
(2015/03/30)

Development of a Rhodium(II)-Catalyzed Chemoselective C(sp3)-H Oxygenation
We report the first example of RhII-catalyzed chemoselective double C(sp3)-H oxygenation, which can directly transform various toluene derivatives into highly valuable aromatic aldehydes with great chemoselectivity and practicality. The critical combination of catalyst Rh(OAc)2, oxidant Selectfluor, and solvents of TFA/TFAA promises the successful delivery of the oxidation with satisfactory yields. A possible mechanism involving a unique carbene-Rh complex is proposed, and has been supported by both experiments and theoretical calculations.
Lin, Yun,Zhu, Lei,Lan, Yu,Rao, Yu
supporting information
p. 14937 - 14942
(2015/10/19)

Highly practical oxidation of benzylic alcohol in continuous-flow system with metal-free catalyst
Oxidation of benzylic alcohol to ketone or aldehyde is one of the most challenging reactions in terms of green chemistry. We report herein that employing H2O2, catalytic amount of Br- and acid in continuous-flow system to realize oxidation of benzylic alcohols with broad substrate scope and high selectivity. More importantly, no over oxidation to acid was obtained and it showed higher selectivity to 2° hydroxyl groups rather than 1°.
Liu, Chengkou,Fang, Zheng,Yang, Zhao,Li, Qingwen,Guo, Shiyu,Zhang, Kai,Ouyang, Pingkai,Guo, Kai
p. 5973 - 5976
(2015/10/28)

Direct catalytic cross-coupling of alkenyllithium compounds
A catalytic method for the direct cross-coupling of alkenyllithium reagents with aryl and alkenyl halides is described. The use of a catalyst comprising Pd2(dba)3/XPhos allows for the stereoselective preparation of a wide variety of substituted alkenes in high yields under mild conditions. In addition (1-ethoxyvinyl)lithium can be efficiently converted into substituted vinyl ethers which, after hydrolysis, give readily access to the corresponding methyl ketones in a one pot procedure.
Hornillos, Valentn,Giannerini, Massimo,Vila, Carlos,Faans-Mastral, Martn,Feringa, Ben L.
p. 1394 - 1398
(2015/02/19)

Highly practical sodium(i)/azobenzene catalyst system for aerobic oxidation of benzylic alcohols
An economic, environmental and practical aerobic oxidation of benzylic alcohols and hetero aryl alcohols to the corresponding carbonyl compounds with good substrate scope is disclosed for the first time. Good to excellent yields were obtained by employing economic and commercially available sodium bromide and a catalytic amount of azobenzene under metal-free and ligand-free conditions. Moreover, aldehydes and acids, the oxidation products of benzylic 1° alcohols, could be obtained using sodium bromide and sodium hydroxide as the co-catalyst respectively in high yields.
Liu, Chengkou,Fang, Zheng,Yang, Zhao,Li, Qingwen,Guo, Shiyu,Guo, Kai
p. 79699 - 79702
(2015/10/06)

Tetra-n-butylammonium bromide: A simple but efficient organocatalyst for alcohol oxidation under mild conditions
A simple but efficient organocatalytic system with 5 mol% tetra-n-butylammonium bromide (TBAB) as the catalyst has been identified for alcohol oxidation for the first time. This organocatalytic system is compatible with a broad range of benzylic/allylic alcohols with various catalytically reactive groups. Besides, it shows excellent selectivity for secondary benzylic alcohols over aliphatic alcohols, and good selectivity over the primary benzylic alcohol site in 4-(1-hydroxyethyl)benzyl alcohol. Thus, the features of simplicity, high efficiency, selectivity and mildness of reaction conditions associated with this TBAB organocatalytic system suggest its potential for widespread use in synthetic chemistry.
Ma, Xinyi,Li, Zhongfeng,Liu, Feijie,Cao, Shengli,Rao, Honghua
supporting information
p. 1741 - 1746
(2014/06/09)

Me2s-induced highly selective reduction of aldehydes in the presence of ketones involving aldehyde-selective rate enhancement: A triruthenium cluster-catalyzed hydrosilylation
Addition of appropriate amounts of Me2S unusually accelerated the hydrosilylation of aldehydes catalyzed by [Ru3(CO)7(Acy)] (1, Acy: μ3-η2,η3,η5-acenaphthylene). The reduction of
Yumino, Shohei,Hashimoto, Toru,Tahara, Atsushi,Nagashima, Hideo
p. 1829 - 1831
(2015/02/19)

Palladium-catalyzed formylation of aryl halides with tert -butyl isocyanide
A novel palladium-catalyzed formylation of aryl halides with isocyanide in the presence of Et3SiH has been demonstrated, which provides a strategy toward important aldehydes with moderate to excellent yield. The advantage of this reaction includes milder conditions, convenient operation, lower toxicity, and wide functional group tolerance.
Jiang, Xiao,Wang, Jin-Mei,Zhang, Ying,Chen, Zhong,Zhu, Yong-Ming,Ji, Shun-Jun
supporting information
p. 3492 - 3495
(2014/07/21)

A crystalline porous coordination polymer decorated with nitroxyl radicals catalyzes aerobic oxidation of alcohols
A porous coordination polymer (PCP) has been synthesized employing an organic ligand in which a stable free radical, isoindoline nitroxide, is incorporated. The crystalline PCP possesses one-dimensional channels decorated with the nitroxyl catalytic sites. When O2 gas or air was used as the oxidant, this PCP was verified to be an efficient, recyclable, and widely applicable catalyst for selective oxidation of various alcohols to the corresponding aldehydes or ketones.
Li, Liangchun,Matsuda, Ryotaro,Tanaka, Iku,Sato, Hiroshi,Kanoo, Prakash,Jeon, Hyung Joon,Foo, Maw Lin,Wakamiya, Atsushi,Murata, Yasujiro,Kitagawa, Susumu
supporting information
p. 7543 - 7546
(2014/06/10)

Diphosphino-functionalised MCM-41-supported palladium complex: An efficient and recyclable catalyst for the formylation of aryl halides
The heterogeneous formylation of aryl halides with HCO2Na at atmospheric pressure by carbon monoxide was readily achieved in the presence of the diphosphino-functionalised MCM-41-supported palladium complex in DMF to afford the corresponding aromatic aldehydes in good to excellent yields. This heterogeneous palladium catalyst can be recovered by simple filtration and reused 10 times without any loss of activity.
Jiang, Jianwen,Wang, Pingping,Cai, Mingzhong
p. 218 - 222
(2014/05/06)

A phosphine-free heterogeneous formylation of aryl halides catalyzed by a thioether-functionalized MCM-41-immobilized palladium complex
Thioether-functionalized MCM-41-immobilized palladium(II) complex [MCM-41-S-PdCl2] was found to be a highly efficient catalyst for the formylation of aryl iodides or bromides with CO (1 atm) using HCO2Na as a hydrogen source. This phosphine-free heterogeneous palladium complex can be easily recovered by simple filtration and reused for at least 10 consecutive trials without any decreases in activity.
Hao, Wenyan,Ding, Guodong,Cai, Mingzhong
p. 53 - 57
(2014/05/06)

Selective oxidations of activated alcohols in water at room temperature
Allylic and benzylic alcohols can be selectively oxidized to their corresponding aldehydes or ketones in water containing nanoreactors composed of the designer surfactant TPGS-750-M. The oxidation relies on catalytic amounts of CuBr, bpy, and TEMPO, with N-methyl-imidazole; air is the stoichiometric oxidant. the Partner Organisations 2014.
Lipshutz,Hageman,Fennewald,Linstadt,Slack,Voigtritter
supporting information
p. 11378 - 11381
(2014/11/08)

Aerobic oxidation and oxidative bromination in aqueous medium using polymer anchored oxovanadium complex
Polymer anchored oxovanadium catalyst was synthesized and characterized. Its catalytic activity was evaluated for the oxidation of various primary and secondary alcohols with molecular oxygen under mild reaction conditions. This catalyst was also effective for the oxidative bromination reaction of organic substrates with 90-100% selectivity of mono substituted products with H 2O2/KBr at room temperature. The above reactions require low temperature, short time period and most importantly all the above reactions occur in aqueous medium. The developed catalyst can be facilely recovered and reused six times without significant decrease in activity and selectivity. 2014 Elsevier B.V. All rights reserved.
Islam, Sk. Manirul,Molla, Rostam Ali,Roy, Anupam Singha,Ghosh, Kajari,Salam, Noor,Iqubal, Md. Asif,Tuhina
p. 169 - 178
(2014/05/06)

Methodology for in situ protection of aldehydes and ketones using trimethylsilyl trifluoromethanesulfonate and phosphines: Selective alkylation and reduction of ketones, esters, amides, and nitriles
A methodology for selective transformations of ketones, esters, Weinreb amides, and nitriles in the presence of aldehydes has been developed. The use of a combination of PPh3-trimethylsilyl trifluoromethanesulfonate (TMSOTf) promotes selective transformation of aldehydes to their corresponding, temporarily protected, O,P-acetal type phosphonium salts. Because, hydrolytic work-up following ensuing reactions of other carbonyl moieties in the substrates liberates the aldehyde moiety, a sequence involving aldehyde protection, transformation of other carbonyl groups, and deprotection can be accomplished in a one-pot manner. Furthermore, the use of PEt3 instead of PPh 3 enables ketones to be converted in situ to their corresponding O,P-ketal type phosphonium salts and, consequently, selective transformations of esters, Weinreb amides, and nitriles in the presence of ketones can be performed. This methodology is applicable to various dicarbonyl compounds, including substrates that possess heteroaromatic skeletons and hydroxyl protecting groups.
Yahata, Kenzo,Minami, Masaki,Yoshikawa, Yuki,Watanabe, Kei,Fujioka, Hiromichi
p. 1298 - 1307
(2014/01/06)

Redox-selective generation of aldehydes and H2 from alcohols under visible light
Photosynthetic dehydrogenation: Potential usefulness of visible-light-induced dehydrogenation of alcohols in organic synthesis was demonstrated, in which aldehydes and H2 were afforded by using Ru/SrTiO3:Rh and water (see scheme). Water was essential for the reaction. High efficiency (TON: up to 15 400 based on Rh; H2 and aldehyde evenly generated) and high selectivity were achieved. Copyright
Liu, Zijun,Caner, Joaquim,Kudo, Akihiko,Naka, Hiroshi,Saito, Susumu
p. 9452 - 9456
(2013/07/26)

Ultrasound assisted the chemoselective 1,1-diacetate protection and deprotection of aldehydes catalyzed by poly(4-vinylpyridinium)hydrogen sulfate salt as a eco-benign, efficient and reusable solid acid catalyst
Poly(4-vinylpyridinium) hydrogen sulfate solid acid was found to be efficient catalyst for preparation of 1,1-diacetate using ultrasound irradiation at ambient temperature and neat condition. Deprotection of the resulting 1,1-diacetates were achieved using the same catalyst in methanol solvent under ultrasound irradiation at room temperature. This new method consistently has the advantage of excellent yields and short reaction times. Utilization of solvent free, simple reaction conditions, isolation, and purification makes this manipulation very interesting from an economic and environmental perspective. Further, the catalyst can be reused and recovered for several times.
Khaligh, Nader Ghaffari,Shirini, Farhad
supporting information
p. 19 - 25
(2013/01/15)

RuCl 3-DCHA catalyst system: A selective aerobic oxidation of primary benzylic alcohols under mild conditions
The aerobic oxidation of benzylic alcohols to their corresponding aldehydes was performed in a RuCl3 · 3H2O-dicyclohexylamine (DCHA) catalyst system under ambient atmosphere at room temperature. It is noteworthy that the RuCl3 · 3H2O-DCHA system displayed a preference for the primary versus secondary benzylic alcohols in both intermolecular and intramolecular competition experiments.
Yu, Kaihui,Ye, Dongnai,Shu, Lei,Zhang, Shiyong,Hu, Qiaosheng,Liu, Liangxian
experimental part
p. 2318 - 2326
(2012/06/18)

Introduction of N-sulfonic acid poly(4-vinylpyridinum) chloride as an efficient and reusable catalyst for the chemoselective 1,1-diacetate protection and deprotection of aldehydes
N-sulfonic acid poly(4-vinylpyridinium) chloride is easily prepared by the reaction of poly(4-vinylpyridine) with neat chlorosulfonic acid. This reagent can be used as an efficient catalyst for the preparation of 1,1-diacetates at room temperature and neat condition. Deprotection of the resulting 1,1-diacetates can also be achieved using the same catalyst in methanol. This new method consistently has the advantages of excellent yields and short reaction times. Further, the catalyst can be reused and recovered for several times.
Shirini, Farhad,Jolodar, Omid Goli
experimental part
p. 61 - 69
(2012/04/17)

Highly practical copper(I)/TEMPO catalyst system for chemoselective aerobic oxidation of primary alcohols
Aerobic oxidation reactions have been the focus of considerable attention, but their use in mainstream organic chemistry has been constrained by limitations in their synthetic scope and by practical factors, such as the use of pure O2 as the oxidant or complex catalyst synthesis. Here, we report a new (bpy)CuI/TEMPO catalyst system that enables efficient and selective aerobic oxidation of a broad range of primary alcohols, including allylic, benzylic, and aliphatic derivatives, to the corresponding aldehydes using readily available reagents, at room temperature with ambient air as the oxidant. The catalyst system is compatible with a wide range of functional groups and the high selectivity for 1° alcohols enables selective oxidation of diols that lack protecting groups.
Hoover, Jessica M.,Stahl, Shannon S.
supporting information; experimental part
p. 16901 - 16910
(2011/12/04)

Triplet-sensitized photoreactivity of a geminal diazidoalkane
Photolysis of 1 in chloroform yielded 2 as the major product and a small quantity of 3. Laser flash photolysis demonstrated that upon irradiation, the first excited triplet state of the ketone (T1K) of 1 is formed and decayed to form radical 4, which has a λmax at 380 nm (t = 2 μs). Radical 4 expelled a nitrogen molecule to yield imine radical 5 (λmax at 300 nm). Density functional theory (DFT) calculations showed that the transition state barrier for the formation of 5 is approximately 4 kcal/mol. In comparison, photolysis of 1 in argon matrices resulted in triplet nitrene 6, which was further characterized with 15N and D isotope labeling and DFT calculations. Prolonged irradiation of 6 yields triplet imine nitrene 7.
Upul Ranaweera, Ranaweera A. A.,Sankaranarayanan, Jagadis,Casey, Lydia,Ault, Bruce S.,Gudmundsdottir, Anna D.
p. 8177 - 8188
(2011/12/22)