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α-Hydroxylation of α,α-Disubstituted N-tert-Butanesulfinyl Ketimines with Molecular Oxygen: Stereoselective Synthesis of α-Tertiary Hydroxyimines
α-Tertiary hydroxyimines were stereoselectively synthesized from enantioenriched N-tert-butanesulfinyl ketimines using potassium tert-butoxide, molecular oxygen, and trimethyl phosphite. The stereoselective hydroxylation of acyclic ketimines bearing two sterically similar α-substituents was achieved by controlling the geometry of the metalloenamine intermediates and the facial selectivity of hydroxylation. The synthetic utility of the resulting α-tertiary hydroxyimines was demonstrated through the successful diastereoselective synthesis of highly substituted β-amino alcohols.
Liu, Hui,Lu, Chong-Dao,Yao, Yun,Yisimayili, Nuermaimaiti
supporting information

(2022/01/20)

Photoredox/nickel-catalyzed hydroacylation of ethylene with aromatic acids
We report a general, practical and scalable hydroacylation reaction of ethylene with aromatic carboxylic acids with the synergistic combination of nickel and photoredox catalysis. Under ambient temperature and pressure, feedstock chemicals such as ethylene can be converted into high-value-added aromatic ketones in moderate to good yields (up to 92%) with reaction time of 2-6 hours.
Chen, Shuai,He, Hengchi,Li, Weipeng,Xie, Jin,Zhang, Lili,Zhu, Chengjian
supporting information
p. 9064 - 9067
(2021/09/15)

Metal-Organic Framework Based on Heptanuclear Cu-O Clusters and Its Application as a Recyclable Photocatalyst for Stepwise Selective Catalysis
Visible-light driven photoreactions using metal-organic frameworks (MOFs) as catalysts are promising with regard to their environmental friendly features such as the use of renewable and sustainable energy of visible light and potential catalyst recyclability. To develop potential heterogeneous photocatalysts, a family of three copper(II) coordination polymers bearing different Cu-O assemblies have been synthesized with the ligand 4,4-disulfo-[1,1-biphenyl]-2,2-dicarboxylate acid (H4DSDC), namely, {[Cu7(DSDC)2(OH)6(H2O)10]·xH2O}n (1), {[Cu4(DSDC)(4,4-bpy)2(OH)4]·2H2O}n (2), and {Cu2(DSDC)(phen)2(H2O)2}n (3) (4,4-bpy = 4,4-bipyridine and phen = 1,10-phenanthroline). Complex 1 represents a metal-organic framework featuring a NbO type topology constructed from the infinite linkage of heptanuclear [Cu7(μ3-OH)6(H2O)10]8+ clusters by deprotonated DSDC4- ligands, comprising one-dimensional hexagonal channels of a diameter around 11 ? that are filled with water molecules. The infinite waving {[Cu2(OH)2]2+}n ladderlike chains in complex 2 are bridged by DSDC4- and 4,4-bpy ligands into a three-dimensional framework. A two-dimensional layered structure is formed in complex 3 due to the existence of terminal phenanthroline ligands. All of the coordination polymers 1-3 are able to catalyze the visible-light driven oxidation of alcohols at mild conditions using hydrogen peroxide as an oxidant, in which complex 1 demonstrates satisfactory efficiency. Significantly for this photoreaction catalyzed by 1, the extent of oxidation over aryl primary alcohols is fully controllable with time-resolved product selectivity, giving either corresponding aldehydes or carboxylate acids in good yields. It is also remarkable that the photocatalyst could be recovered almost quantitatively on completion of the catalytic cycle without any structure change, and could be recycled for catalytic use for at least five cycles with constant efficiency. This photocatalyst with time-resolved selectivity for different products may provide new insight into the design and development of novel catalytic systems.
Zhou, Jie,Huang-Fu, Xu,Huang, Yang-Ying,Cao, Chu-Ning,Han, Jie,Zhao, Xiao-Li,Chen, Xu-Dong
p. 254 - 263
(2019/12/04)

Combination of organocatalytic oxidation of alcohols and organolithium chemistry (RLi) in aqueous media, at room temperature and under aerobic conditions
A tandem protocol to access tertiary alcohols has been developed which combines the organocatalytic oxidation of secondary alcohols to ketones followed by their chemoselective addition by several RLi reagents. Reactions take place at room temperature, under air and in aqueous solutions, a trio of conditions that are typically forbidden in polar organometallic chemistry.
Elorriaga, David,García-álvarez, Joaquín,González-Sabín, Javier,Hevia, Eva,Morís, Francisco,Presa Soto, Alejandro,Ríos-Lombardía, Nicolás,Rodríguez-álvarez, María Jesús
supporting information
p. 8932 - 8935
(2020/08/17)

Cobalt-Catalyzed Reductive C-O Bond Cleavage of Lignin β-O-4 Ketone Models via in Situ Generation of the Cobalt-Boryl Species
An efficient and mild method for reductive C-O bond cleavage of lignin β-O-4 ketone models was developed to afford the corresponding ketones and phenols with PDI-CoCl2 as the precatalyst and diboron reagent as the reductant. The synthetic utility of the methodology was demonstrated by depolymerization of a polymeric model and gram-scale transformation. Mechanistic studies suggested that this transformation involves steps of carbonyl insertion, 1,2-Brook type rearrangement, β-oxygen elimination, and rate-limiting regeneration of the catalytic active Co-B species.
Gao, Kecheng,Xu, Man,Cai, Cheng,Ding, Yanghao,Chen, Jianhui,Liu, Bosheng,Xia, Yuanzhi
p. 6055 - 6060
(2020/08/12)

A silver-catalyzed radical ring-opening reaction of cyclopropanols with sulfonyl oxime ethers
A silver-catalyzed ring-opening reaction of cyclopropanols with sulfonyl oxime ethers has been developed. The protocol was conducted under mild reaction conditions to provide a series of ?-keto oxime ethers with moderate to good yields. The reaction proceeded in a stereoselective manner for CF3-containing oxime ethers to provide a single stereoisomer, while an inseparableEandZmixture was obtained for CN-containing oxime ethers. Mechanistic studies indicate that the reaction proceededviaa radical mechanism.
Wang, Xin,Zeng, Xiaobao,Zhang, Yanan,Zhao, Yu,Zhu, Li
supporting information
p. 3734 - 3739
(2020/06/03)

Loxoprofen derivative
The invention provides a Loxoprofen derivative shown in the following formula (I). R1 is hydrogen atoms or substituted or non-substituted alkyl, R2 is substituted or non-substituted alkyl, the Loxoprofen derivative has low gastrointestinal tract side effects, and the bioavailability can be improved. The formula (I) is shown in the specification.
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Paragraph 0036; 0037; 0039; 0040

(2019/01/23)

Novel benzene-based carbamates for ache/bche inhibition: Synthesis and ligand/structure-oriented sar study
A series of new benzene-based derivatives was designed, synthesized and comprehensively characterized. All of the tested compounds were evaluated for their in vitro ability to potentially inhibit the acetyl-and butyrylcholinesterase enzymes. The selectivity index of individual molecules to cholinesterases was also determined. Generally, the inhibitory potency was stronger against butyryl-compared to acetylcholinesterase; however, some of the compounds showed a promising inhibition of both enzymes. In fact, two compounds (23, benzyl ethyl(1-oxo-1-phenylpropan-2-yl)carbamate and 28, benzyl (1-(3-chlorophenyl)-1-oxopropan-2-yl) (methyl)carbamate) had a very high selectivity index, while the second one (28) reached the lowest inhibitory concentration IC50 value, which corresponds quite well with galanthamine. Moreover, comparative receptor-independent and receptor-dependent structure–activity studies were conducted to explain the observed variations in inhibiting the potential of the investigated carbamate series. The principal objective of the ligand-based study was to comparatively analyze the molecular surface to gain insight into the electronic and/or steric factors that govern the ability to inhibit enzyme activities. The spatial distribution of potentially important steric and electrostatic factors was determined using the probability-guided pharmacophore mapping procedure, which is based on the iterative variable elimination method. Additionally, planar and spatial maps of the host–target interactions were created for all of the active compounds and compared with the drug molecules using the docking methodology.
Bak, Andrzej,Kozik, Violetta,Kozakiewicz, Dariusz,Gajcy, Kamila,Strub, Daniel Jan,Swietlicka, Aleksandra,Stepankova, Sarka,Imramovsky, Ales,Polanski, Jaroslaw,Smolinski, Adam,Jampilek, Josef
(2019/05/10)

Electrochemical performance of ABNO for oxidation of secondary alcohols in acetonitrile solution
The ketones was successfully prepared from secondary alcohols using 9-azabicyclo[3.3.1]nonane-N-oxyl (ABNO) as the catalyst and 2,6-lutidine as the base in acetonitrile solution. The electrochemical activity of ABNO for oxidation of 1-phenylethanol was investigated by cyclic voltammetry, in situ Fourier transform infrared spectroscopy (FTIR) and constant current electrolysis experiments. The resulting cyclic voltammetry indicated that ABNO exhibited much higher electrochemical activity when compared with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) under the similar conditions. A reasonable reaction mechanism of the electrocatalytic oxidation of 1-phenylethanol to acetophenone was proposed. In addition, a series of secondary alcohols could be converted to the corresponding ketones at room temperature in 80-95% isolated yields.
Niu, Pengfei,Liu, Xin,Shen, Zhenlu,Li, Meichao
(2019/01/14)

Manganese PNP-pincer catalyzed isomerization of allylic/homo-allylic alcohols to ketones-activity, selectivity, efficiency
We report the first manganese catalyzed isomerization of allylic alcohols to produce the corresponding carbonyl compounds. The ligand plays a decisive role in the efficiency of this reaction. Very high conversions could be obtained using a solvent-free reaction system. A detailed DFT study reveals a self-dehydrogenation/hydrogenation reaction mechanism which was verified by the isolation of the α,β-unsaturated ketone as intermediate and a deuterium labeling experiment. It also provided a rationale for the observed selectivity and the higher efficiency of phenyl over isopropyl substitution.
Xia, Tian,Spiegelberg, Brian,Wei, Zhihong,Jiao, Haijun,Tin, Sergey,Hinze, Sandra,De Vries, Johannes G.
p. 6327 - 6334
(2019/11/20)

Ruthenium-Catalyzed Redox Isomerizations inside Living Cells
Tailored ruthenium(IV) complexes can catalyze the isomerization of allylic alcohols into saturated carbonyl derivatives under physiologically relevant conditions, and even inside living mammalian cells. The reaction, which involves ruthenium-hydride intermediates, is bioorthogonal and biocompatible, and can be used for the "in cellulo" generation of fluorescent and bioactive probes. Overall, our research reveals a novel metal-based tool for cellular intervention, and comes to further demonstrate the compatibility of organometallic mechanisms with the complex environment of cells.
Vidal, Cristian,Tomás-Gamasa, María,Gutiérrez-González, Alejandro,Mascarenas, José L.
supporting information
p. 5125 - 5129
(2019/03/29)

A Deoximation Method for Deprotection of Ketones and Aldhydes Using a Graphene-Oxide-Based Co-catalysts System
The deoximation of a wide range of ketoximes and aldoximes to their corresponding carbonyl compounds with high yields has been achieved using graphene oxide (GO) and sodium nitrite (NaNO2) as highly efficient catalysts and air as the green oxidant under mild conditions. The mechanism of deprotection and recycling use of catalyst were revealed in deep experiment. The carboxylic acid groups on the GO were essential for high catalytic activity. (Figure presented.).
Tong, Qiaolin,Liu, Yang,Gao, Xuezhi,Fan, Zhanfang,Liu, Tianfu,Li, Bo,Su, Dangsheng,Wang, Qinghe,Cheng, Maosheng
supporting information
p. 3137 - 3145
(2019/05/01)

One-Pot Transformation of Ketoximes into Optically Active Alcohols and Amines by Sequential Action of Laccases and Ketoreductases or ω-Transaminases
An enzymatic one-pot process for asymmetric transformation of prochiral ketoximes into alcohols or amines was developed by sequential coupling of a laccase-catalyzed deoximation either with a ketone reduction (ketoreductase, KRED) or bioamination (ω-transaminase, ω-TA) in aqueous medium. An accurate selection of biocatalysts provided the corresponding products in excellent enantiomeric excesses and overall conversions ranging from 83 to >99 % for alcohols and 70 to >99 % for amines. Likewise, the employment of exclusively 1 % (w/w) of Cremophor, a polyethoxylated castor oil, as co-solvent enabled to reach concentrations up to 100 mM in the chiral alcohols cascade.
Correia Cordeiro, Raquel S.,Ríos-Lombardía, Nicolás,Morís, Francisco,Kourist, Robert,González-Sabín, Javier
p. 1272 - 1277
(2019/01/24)

Isomerization of Allylic Alcohols to Ketones Catalyzed by Well-Defined Iron PNP Pincer Catalysts
[Fe(PNP)(CO)HCl] (PNP=di-(2-diisopropylphosphanyl-ethyl)amine), activated in situ with KOtBu, is a highly active catalyst for the isomerization of allylic alcohols to ketones without an external hydrogen supply. High reaction rates were obtained at 80 °C, but the catalyst is also sufficiently active at room temperature with most substrates. The reaction follows a self-hydrogen-borrowing mechanism, as verified by DFT calculations. An alternative isomerization through alkene insertion and β-hydride elimination could be excluded on the basis of a much higher barrier. In alcoholic solvents, the ketone product is further reduced to the saturated alcohol.
Xia, Tian,Wei, Zhihong,Spiegelberg, Brian,Jiao, Haijun,Hinze, Sandra,de Vries, Johannes G.
supporting information
p. 4043 - 4049
(2018/01/27)

Programming cascade reactions interfacing biocatalysis with transition-metal catalysis in: Deep Eutectic Solvents as biorenewable reaction media
The first application of Deep Eutectic Solvents (DESs) in the asymmetric bioreduction of ketones has been accomplished for purified ketoreductases (KREDs). The performance of the biocatalysts was enhanced by increasing the percentage of neoteric solvent in DES-buffer mixtures. At a buffer content of 50% (w/w) and even 20% (w/w), the combination of either choline chloride (ChCl)/glycerol (Gly) (1:2) or ChCl/sorbitol (1:1) proved to be most effective for achieving up to >99% conversion and up to >99% enantiomeric excess of the corresponding secondary alcohols. Moreover, this reaction medium was used to perform the first example of a chemoenzymatic cascade process in DES-buffer mixtures, namely the ruthenium-catalysed isomerisation of racemic allylic alcohols coupled with a further enantioselective bioreduction, in both sequential and concurrent modes.
Cicco, Luciana,Ríos-Lombardía, Nicolás,Rodríguez-álvarez, María J.,Morís, Francisco,Perna, Filippo M.,Capriati, Vito,García-álvarez, Joaquín,González-Sabín, Javier
supporting information
p. 3468 - 3475
(2018/08/07)

Fe(NO3)3·9H2O-catalyzed aerobic oxidative deoximation of ketoximes and aldoximes under mild conditions
A mild, simple process for the effective aerobic oxidative deoximation of a wide range of ketoximes and aldoximes has been developed that utilizes Fe(NO3)3·9H2O as the single catalyst and molecular oxygen as the green oxidant. The environmentally benign protocol provides moderate to excellent yield and broad functional groups tolerance and is a valuable synthetic method for practical applications. According the relevant verification experiment, a plausible mechanism has been proposed.
Li, Yongshu,Xu, Nizhou,Mei, Guangyao,Zhao, Yun,Zhao, Yiyong,Lyu, Jinghui,Zhang, Guofu,Ding, Chengrong
supporting information
p. 810 - 814
(2018/08/09)

Solvent free, light induced 1,2-bromine shift reaction of α-bromo ketones
Photolysis of α-bromopropiophenones in acetonitrile results in formation of β-bromopropiophenones with good product selectivity, which can be coined as 1,2-Br shift reaction. The product selectivity increases when the reaction is done in neat or solid state, where only the 1,2-Br shift product is formed in some cases. The reaction is suggested to proceed by C–Br bond homolysis to give a radical pair, followed by disproportionation and conjugate addition of HBr to the α,β-unsaturated ketone intermediate. When the unsaturated intermediate is stabilized by an extra conjugation, the reaction stops at the stage, in which the unsaturated ketone becomes a major product. The synthetic method described in this research fits in a category of eco-friendly organic synthesis nicely since the reaction does not use volatile organic solvents and any other additives such as acid, base or metal catalysts, etc. Besides, the method fits into perfect atom economy, which does not give any side products. The synthetic method should find much advantage over other alternative methods to obtain β-bromo carbonyl compounds.
An, Sejin,Moon, Da Yoon,Park, Bong Ser
p. 6922 - 6928
(2018/10/24)

Nickel-Catalyzed Addition of Arylboronic Acids to Alkyl Nitriles for Synthesis of Aryl Ketones in Fluorinated Solvent
A mild and efficient nickel-catalyzed addition of arylboronic acids to alkyl nitriles in a fluorinated solvent for the synthesis of various aryl ketones is described. A broad range of arylboronic acids and alkyl nitriles were investigated, and the desired products were obtained with good to excellent yields under the optimized conditions. This method provides an opportunity for the synthesis of aryl ketones from alkyl nitriles, especially acetonitrile, with a non-noble metal catalyst in one pot.
Tu, Dong-Huai,Li, Yang,Zhao, Bo,Gu, Yu-Jie,Wang, Bo,Lu, Ju-You,Lu, Jian
supporting information
p. 593 - 596
(2017/12/06)

Thiyl radical promoted chemo- and regioselective oxidation of CC bonds using molecular oxygen: Via iron catalysis
The first example of the thiyl radical promoted ligand-free iron-catalyzed oxidative cleavage of alkenes using molecular oxygen (1 atm) has been developed. The reaction proceeds under mild reaction conditions with high efficiency and high chemo- and regioselectivity. It features a broad substrate scope and excellent functional group compatibility, enabling facile access to valuable molecules for application in medicinal chemistry. Preliminary mechanistic studies reveal that a vital intermediate dioxetane might be involved in the reaction and a thiyl radical plays a synergistic role in facilitating the selective oxidation of the CC bond.
Xiong, Baojian,Zeng, Xiaoqin,Geng, Shasha,Chen, Shuo,He, Yun,Feng, Zhang
supporting information
p. 4521 - 4527
(2018/10/17)

Ni/Ti Dual Catalytic Cross-Coupling of Nitriles and Organobromides to Access Ketones
Herein, we report the development of a dual catalytic approach for the cross-coupling of nitriles with aryl- and aliphatic-bromides. A titanium(III) catalyst is used to activate nitriles enabling their coupling with organobromides through a nickel catalyst. The Ni/Ti system efficiently prepared unsymmetrical ketones with good chemoselectivity and could selectively couple a bromide in the presence of other functionalizable handles.
Chenniappan, Vinoth Kumar,Silwal, Sajan,Rahaim, Ronald J.
p. 4539 - 4544
(2018/05/23)

Aerobic oxidation of secondary alcohols in water with ABNO/tert-butyl nitrite/KPF6catalytic system
A green and efficient transition-metal free ABNO/tert-butyl nitrite/KPF6-catalyzed aerobic oxidation of secondary alcohols in water has been achieved. Under the optimal reaction conditions, a number of secondary aliphatic alcohols and secondary benzylic alcohols can be converted to their corresponding ketones in excellent yields (up to 99%).
Ma, Jiaqi,Hong, Chao,Wan, Yan,Li, Meichao,Hu, Xinquan,Mo, Weimin,Hu, Baoxiang,Sun, Nan,Jin, Liqun,Shen, Zhenlu
p. 652 - 657
(2017/01/25)

Chloramine-T-mediated oxidation of benzylic alcohols using indium(III) triflate
The efficient oxidation of benzylic alcohols to carbonyl compounds was performed using chloramine-T and a catalytic amount of indium(III) triflate. The primary benzylic alcohols were converted to the corresponding aldehydes in a good yield, and the secondary benzylic alcohols were oxidized to ketones in a high yield. The optimized reaction conditions required 0.3eq of indium(III) triflate and the use of acetonitrile as a solvent.
Nakahara, Kazuhide,Kitazawa, Chie,Mineno, Tomoko
p. 801 - 804
(2017/08/09)

Alcohol Oxidations Using Reduced Polyoxovanadates
A full account of our recently communicated room temperature alcohol oxidation using reduced polyoxovanadates (r-POVs) is presented. Extensive optimizations revealed optimal conditions employing 0.02 equiv. of r-POV catalyst Cs5(V14As8O42Cl), 5 equiv. tert-butyl hydrogen peroxide (tBuOOH) as the terminal co-oxidant, in an acetone solvent for the quantitative oxidation of aryl-substituted secondary alcohols to their ketone products. The substrate scope tolerates most aryl substituted secondary alcohols in good to quantitative yields while alkyl secondary and primary activated alcohols were sluggish in comparison under similar conditions. Catalyst recyclability was successful on a 1.0?mmol scale of starting alcohol 1-phenylethanol. The oxidation was also successfully promoted by the VIV/VV mixed valent polyoxovanadate (POV) Cs11Na3Cl5(V15O36Cl). Finally, a third POV, Cs2.64(V5O9)(AsO4)2, was investigated for catalytic activity using our established reaction protocol, but proved ineffective as compared to the other two r-POV catalysts. This study expands the field of POM-mediated alcohol oxidations to include underexplored r-POV catalysts. While our catalysts do not supplant the best catalysts known for the transformation, their study may inform the development of other novel oxidative transformations mediated by r-POVs.
Campbell, McKenzie L.,Sulejmanovic, Dino,Schiller, Jacqueline B.,Turner, Emily M.,Hwu, Shiou-Jyh,Whitehead, Daniel C.
(2017/03/20)

Efficient acceptorless dehydrogenation of secondary alcohols to ketones mediated by a PNN-Ru(II) catalyst
Four types of ruthenium(II) complexes, [fac-PNN]RuH(PPh3)(CO) (A), [fac-PNHN]RuH(η1-BH4)(CO) (B), [fac-PNHN]RuCl2(PPh3) (C) and [fac-PNHN]RuH(η1-BH4)(PPh3) (D) (where PNHN and PNN are N-(2-(diphenylphosphino)ethyl)-5,6,7,8-tetrahydroquinoline-8-amine and its deprotonated derivative), have been synthesized and assessed as catalysts for the acceptorless dehydrogenation of secondary alcohols to afford ketones. It was found that C, in combination with t-BuOK, proved the most effective and versatile catalyst allowing aromatic-, aliphatic- and cycloalkyl-containing alcohols to be efficiently converted to their corresponding ketones with particularly high values of TON achievable. Furthermore, the mechanism for this PNN-Ru mediated process been proposed on the basis of a number of intermediates that have been characterized by EI-MS and NMR spectroscopy. These catalysts show great potential for applications in atom-economic synthesis as well as in the development of organic hydride-based hydrogen storage systems.
Wang, Zheng,Pan, Bing,Liu, Qingbin,Yue, Erlin,Solan, Gregory A.,Ma, Yanping,Sun, Wen-Hua
p. 1654 - 1661
(2017/07/13)

KOtBu-Mediated Domino Isomerization and Functionalization of Aromatic Allylic Alcohols
Transition-metal- as well as ligand-free base-mediated domino isomerization and alkylation of allylic alcohols is presented. This protocol features the conversion of simple allylic alcohols into the corresponding ketones through isomerization in the presence of a simple base. Significantly, these in situ generated ketones subsequently undergo alkylation with styrenes as electrophiles, in a domino one-pot fashion, as an atom- and step-economical chemical process.
Suchand, Basuli,Satyanarayana, Gedu
p. 3886 - 3895
(2017/07/22)

One-pot sustainable synthesis of tertiary alcohols by combining ruthenium-catalysed isomerisation of allylic alcohols and chemoselective addition of polar organometallic reagents in deep eutectic solvents
Ru(iv)-Catalysed redox isomerisation of allylic alcohols has, for the first time, been successfully assembled with the chemoselective addition of organolithium or organomagnesium reagents to the in situ formed ketones, en route to tertiary alcohols, employing deep eutectic solvents as environmentally friendly reaction media. The overall transformation, which formally involves three consecutive and different steps such as (i) the reduction of a C-C double bond, (ii) the oxidation of a secondary carbinol moiety, and (iii) a chemoselective C-C bond formation, takes place in protic and biorenewable eutectic mixtures in a sequential one-pot fashion using a commercially and easily available catalytic system, with excellent conversions (up to 99% yield), at room temperature and under air in the last step, with no concomitant reduction or enolisation processes, and with high atom economy, in agreement with the principles of the so-called green chemistry.
Cicco, Luciana,Rodríguez-álvarez, María J.,Perna, Filippo M.,García-álvarez, Joaquín,Capriati, Vito
supporting information
p. 3069 - 3077
(2017/07/24)

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)

Iron/ABNO-Catalyzed Aerobic Oxidation of Alcohols to Aldehydes and Ketones under Ambient Atmosphere
We report a new Fe(NO3)3·9H2O/9-azabicyclo[3.3.1]nonan-N-oxyl catalyst system that enables efficient aerobic oxidation of a broad range of primary and secondary alcohols to the corresponding aldehydes and ketones at room temperature with ambient air as the oxidant. The catalyst system exhibits excellent activity and selectivity for primary aliphatic alcohol oxidation. This procedure can also be scaled up. Kinetic analysis demonstrates that C-H bond cleavage is the rate-determining step and that cationic species are involved in the reaction.
Wang, Lianyue,Shang, SenSen,Li, Guosong,Ren, Lanhui,Lv, Ying,Gao, Shuang
p. 2189 - 2193
(2016/03/15)

Room-temperature catalytic oxidation of alcohols with the polyoxovanadate salt Cs5(V14As8O42Cl)
While many known methods for oxidation mediated by polyoxometalates (POMs) employ environmentally friendly co-oxidants, they tend to employ large catalyst loadings (e.g. 40 mol%) and costly high reaction temperatures (~90-135 °C) that potentially contribute to the degradation of the catalyst and reduce their effectiveness. Herein, we present some initial results demonstrating a room temperature catalytic oxidation using the reduced salt-inclusion polyoxometalate, Cs5(V14As8O42Cl), that contains polyoxovanadate (POV) clusters as an efficient catalyst (e.g., 2 mol%) in the transformation of secondary alcohols to their corresponding ketones in very good to quantitative yields. Further, the catalyst can be suspended on celite and recycled.
Campbell, McKenzie L.,Sulejmanovic, Dino,Schiller, Jacqueline B.,Turner, Emily M.,Hwu, Shiou-Jyh,Whitehead, Daniel C.
p. 3208 - 3213
(2016/05/24)

From a Sequential to a Concurrent Reaction in Aqueous Medium: Ruthenium-Catalyzed Allylic Alcohol Isomerization and Asymmetric Bioreduction
The ruthenium-catalyzed redox isomerization of allylic alcohols was successfully coupled with the enantioselective enzymatic ketone reduction (mediated by KREDs) in a concurrent process in aqueous medium. The overall transformation, formally the asymmetric reduction of allylic alcohols, took place with excellent conversions and enantioselectivities, under mild reaction conditions, employing commercially and readily available catalytic systems, and without external coenzymes or cofactors. Optimization resulted in a multistep approach and a genuine cascade reaction where the metal catalyst and biocatalyst coexist from the beginning.
Ríos-Lombardía, Nicolás,Vidal, Cristian,Liardo, Elisa,Morís, Francisco,García-álvarez, Joaquín,González-Sabín, Javier
supporting information
p. 8691 - 8695
(2016/07/21)

MAGNETICALLY SEPARABLE IRON-BASED HETEROGENEOUS CATALYSTS FOR DEHYDROGENATION OF ALCOHOLS AND AMINES
The present invention discloses an iron-based nitrogen doped graphene catalyst, process for preparation thereof and use of said catalyst in oxidant-free catalytic dehydrogenation of alcohols and amines to the corresponding carbonyl compounds, amines and N-heterocylic compounds with extraction of molecular hydrogen as the only by-product.
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(2016/12/22)

N-Functionalized Amino Acids Promoted Aerobic Copper-Catalyzed Oxidation of Benzylic Alcohols in Water
Instead of traditional N,N-bidentate ligands, N-functionlized amino acids were used as powerful N,O-bidentate ligands in aerobic copper/TEMPO-catalyzed system for promoting oxidation of benzylic alcohols. Under the optimized reaction conditions, a wide range of primary and secondary benzylic alcohols have been efficiently converted into aldehydes and ketones with good to excellent yields in water.
Zhang, Guofu,Lei, Jie,Han, Xingwang,Luan, Yuxin,Ding, Chengrong,Shan, Shang
p. 779 - 784
(2015/03/30)

Direct conversion of allyl arenes to aryl ethylketones via a TBHP-mediated palladium-catalyzed tandem isomerization-Wacker oxidation of terminal alkenes
A TBHP-mediated palladium-catalyzed tandem isomerization-Wacker oxidation of terminal alkenes was developed. This methodology provides a new efficient and simple route for conversion of a range of allyl arenes directly into aryl ethylketones in good yields with high chemoselectivity.
Zhao, Jinwu,Liu, Li,Xiang, Shijian,Liu, Qiang,Chen, Huoji
p. 5613 - 5616
(2015/05/27)

Transition-Metal-Free Self-Hydrogen-Transferring Allylic Isomerization
Phenanthroline and tert-butoxide have been established as powerful radical initiators in reactions such as the SRN1-type coupling reactions due to the cooperation of large heteroarenes and a special feature of tert-butoxide. The first phenanthroline-tert-butoxide-catalyzed transition-metal-free allylic isomerization is described. The resulting ketones are key intermediates for indenes. The control experiments rule out the base-promoted allylic anion pathway. The radical pathway is supported by experimental evidence that includes kinetic study, kinetic isotope effect, isotope-labeling experiments, trapping experiments, and EPR experiments.
Zheng, Hong-Xing,Xiao, Zu-Feng,Yao, Chuan-Zhi,Li, Qiang-Qiang,Ning, Xiao-Shan,Kang, Yan-Biao,Tang, Yong
supporting information
p. 6102 - 6105
(2016/01/09)

Chemoenzymatic one-pot synthesis in an aqueous medium: combination of metal-catalysed allylic alcohol isomerisation-asymmetric bioamination
The ruthenium-catalysed isomerisation of allylic alcohols was coupled, for the first time, with asymmetric bioamination in a one-pot process in an aqueous medium. In the cases involving prochiral ketones, the ω-TA exhibited excellent enantioselectivity, identical to that observed in the single step. As a result, amines were obtained from allylic alcohols with high overall yields and excellent enantiomeric excesses.
Ríos-Lombardía, Nicolás,Vidal, Cristian,Cocina, María,Morís, Francisco,García-álvarez, Joaquín,González-Sabín, Javier
supporting information
p. 10937 - 10940
(2015/06/30)

Benzyllithiums bearing aldehyde carbonyl groups. A flash chemistry approach
Reductive lithiation of benzyl halides bearing aldehyde carbonyl groups followed by reaction with subsequently added electrophiles was successfully accomplished without affecting the carbonyl groups by taking advantage of short residence times in flow microreactors.
Nagaki, Aiichiro,Tsuchihashi, Yuta,Haraki, Suguru,Yoshida, Jun-ichi
supporting information
p. 7140 - 7145
(2015/07/01)

Role of sterically demanding chiral dirhodium catalysts in site-selective C-H functionalization of activated primary C-H bonds
The influence of sterically demanding dirhodium tetracarboxylate catalysts on the site selectivity of C-H functionalization by means of rhodium carbene-induced C-H insertion is described. The established dirhodium tetraprolinate-catalyzed reactions of aryldiazoacetates cause preferential C-H functionalization of secondary C-H bonds as a result of competing steric and electronic effects. The sterically more demanding dirhodium tetrakis(triarylcyclopropanecarboxylate) catalysts, exemplified by dirhodium tetrakis[(R)-(1-(biphenyl)-2,2-diphenylcyclopropanecarboxylate)] [Rh 2(R-BPCP)4], favor C-H functionalization of activated primary C-H bonds. Highly site-selective and enantioselective C-H functionalization of a variety of simple substrates containing primary benzylic, allylic, and methoxy C-H bonds was achieved with this catalyst. The utility of this approach has been demonstrated by the late-stage primary C-H functionalization of (-)-∝-cedrene and a steroid.
Qin, Changming,Davies, Huw M. L.
supporting information
p. 9792 - 9796
(2014/07/22)

Magnetically recyclable core-shell nanocatalysts for efficient heterogeneous oxidation of alcohols
We describe the designed fabrication of magnetically recyclable core-shell Pd nanocatalysts for the efficient oxidation of alcohols under base-free reaction conditions in water. The Pd NPs that are half-partitioned in the polymer matrix can provide not only high catalytic activity but also stabilization of the nanocatalysts under harsh reaction conditions. Furthermore the magnetic separation provides a convenient method for removing and recycling the active Pd nanocatalysts from the reaction mixture. The designed nanocatalysts can be readily synthesized in a large scale and were able to be reused for five consecutive cycles of the oxidation of cycloheptanol. The nanocatalysts present high catalytic activity in other types of catalytic reactions involving Pd NPs such as Suzuki cross-coupling and reduction of nitroarenes. the Partner Organisations 2014.
Shokouhimehr, Mohammadreza,Shin, Keun-Young,Lee, James S.,Hackett, Michael J.,Jun, Samuel Woojoo,Oh, Myoung Hwan,Jang, Jyongsik,Hyeon, Taeghwan
p. 7593 - 7599
(2014/05/06)

Palladium(II)-catalyzed desulfitative synthesis of aryl ketones from sodium arylsulfinates and nitriles: Scope, limitations, and mechanistic studies
A fast and efficient protocol for the palladium(II)-catalyzed production of aryl ketones from sodium arylsulfinates and various organic nitriles under controlled microwave irradiation has been developed. The wide scope of the reaction has been demonstrated by combining 14 sodium arylsulfinates and 21 nitriles to give 55 examples of aryl ketones. One additional example illustrated that, through the choice of the nitrile reactant, benzofurans are also accessible. The reaction mechanism was investigated by electrospray ionization mass spectrometry and DFT calculations. The desulfitative synthesis of aryl ketones from nitriles was also compared to the corresponding transformation starting from benzoic acids. Comparison of the energy profiles indicates that the free energy requirement for decarboxylation of 2,6-dimethoxybenzoic acid and especially benzoic acid is higher than the corresponding desulfitative process for generating the key aryl palladium intermediate. The palladium(II) intermediates detected by ESI-MS and the DFT calculations provide a detailed understanding of the catalytic cycle. (Figure Presented).
Skillinghaug, Bobo,Sk?ld, Christian,Rydfjord, Jonas,Svensson, Fredrik,Behrends, Malte,S?vmarker, Jonas,Sj?berg, Per J. R.,Larhed, Mats
p. 12018 - 12032
(2015/01/16)

DMF as carbon source: Rh-catalyzed α-methylation of ketones
An unprecedented Rh-catalyzed direct methylation of ketones with N,N-dimethylformamide (DMF) is disclosed. The reaction shows a broad substrate scope, tolerating both aryl and alkyl ketones with various substituents. Mechanistic studies suggest that DMF delivers a methylene fragment followed by a hydride in the methylation process.
Li, Yang,Xue, Dong,Lu, Wei,Wang, Chao,Liu, Zhao-Tie,Xiao, Jianliang
supporting information
p. 66 - 69
(2014/01/23)

Oxidation of alcohols to aldehydes and ketones using selenium ionic liquid
A new type of ionic liquid supported selenium reagents were synthesized and found to be an excellent catalyst in the oxidation of alcohols to aldehydes and ketones in the presence of 30% H2O2. The predictable solubility of ionic liquids allows an easy separation of the oxidation products from the reaction mixture. Furthermore, the oxidation reaction can be carried out using an ionic liquid as the solvent, and the ionic liquid-supported selenium reagents can be recycled and used for four times with a little decrease in catalytic performance.
Cheng, Xian Yi,Li, Kang Feng,Wang, Qiao Jian,Wang, Cong Ying,Ying, Tao Kai
experimental part
p. 801 - 804
(2012/08/13)

Kinetic resolution of aryl alkenylcarbinols catalyzed by Fc-PIP
An effective kinetic resolution of a variety of aryl alkenylcarbinols catalyzed by nonenzymatic acyl transfer catalyst Fc-PIP was developed, affording corresponding unreacted alcohols in good to excellent ee value up to 99% and with selectivity factors up to 24.
Hu, Bin,Meng, Meng,Jiang, Shanshan,Deng, Weiping
scheme or table
p. 1289 - 1294
(2012/08/28)

Synthesis, spectroscopic characterization, and molecular structure of triphenyl butene derivatives containing a cyclopentadienyl iron unit
Three hydroxyl substituted triphenyl butene compounds (PHB) and their derivatives containing a cyclopentadienyl iron (PHB-Fc) unit were efficiently synthesized. The synthesis involved the McMurry cross-coupling reaction of appropriate ketones and the nucleophilic aromatic substitution (SNAr) reaction of (η6-chlorobenzene) (η5- cyclopentadienyl) iron hexafluorophosphate (Fc-Cl). The target compounds were characterized by IR, 1H NMR, 13C NMR, and MS. Their photophysical processes were investigated by UV-Vis absorption and fluorescence emission spectra in acetonitrile. The geometric structure was optimized based on the density functional theory at the B3LYP level. Theoretical results reveal that electron transfer occurred from the HOMO to the LUMO in PHB-Fc. The change in electron distribution subsequently led to the improved second-order optical susceptibility of PHB-Fc.
Han, Junru,Li, Guanglei,Wang, Tao
p. 374 - 379
(2013/01/13)

Nickel-catalyzed Kumada reaction of tosylalkanes with Grignard reagents to produce alkenes and modified arylketones
Open a new door: The first example of alkene synthesis from alkyl electrophiles with Grignard reagents using the Kumada cross-coupling reaction strategy is reported. This method opens a new door for the Kumada cross-coupling reaction, allowing alkenes to be prepared from the reaction of tosylalkanes with Grignard reagents. Copyright
Wu, Ji-Cheng,Gong, Lu-Bing,Xia, Yuanzhi,Song, Ren-Jie,Xie, Ye-Xiang,Li, Jin-Heng
supporting information
p. 9909 - 9913
(2012/10/30)

Facile preparation of aromatic ketones from aromatic bromides and arenes with aldehydes
Aromatic ketones were efficiently prepared in good yields by the reactions of aryl bromides with n-BuLi, followed by the reactions with aromatic aldehydes or aliphatic aldehydes and the subsequent treatment with molecular iodine and K2CO3, in a one-pot method. The same treatment of arenes, instead of aromatic bromides, also provided the corresponding aromatic ketones in good yields. Using these methods, various diaryl ketones and alkyl aryl ketones bearing electron-rich aromatics and electron-deficient aromatics could be prepared efficiently by a simple, transition-metal-free, and therefore environmentally benign experimental procedure.
Ushijima, Sousuke,Dohi, Souya,Moriyama, Katsuhiko,Togo, Hideo
scheme or table
p. 1436 - 1442
(2012/03/09)

Atom efficient Friedel-Crafts acylation of toluene with propionic anhydride over solid mesoporous superacid UDCaT-5
Friedel-Crafts acylation is ubiquitous in industry and is typically carried out by using more than stoichiometric quantities of homogeneous catalysts. This creates pollution. In this work, acylation of toluene was studied in liquid phase with propionic anhydride with a variety of solid superacids to produce 4′-methylpropiophenone (4′-MPP). The solid superacids were modified versions of zirconia, namely, UDCaT-4, UDCaT-5 and UDCaT-6 developed in our laboratory; amongst which UDCaT-5 was the most active, selective and robust catalyst. The effects of various reaction parameters on the rate of reaction and selectivity were investigated to deduce the intrinsic kinetics of the reaction. The reaction is free from any external mass transfer as well as intraparticle diffusion limitations and is intrinsically kinetically controlled. The acylation conditions were: temperature 180 °C, toluene to propionic anhydride molar ratio 5:1, catalyst loading 0.06 g cm-3, speed of agitation 1000 rpm, under autogenous pressure in a stainless steel autoclave reactor. Propionic acid generated in situ also reacts sequentially with toluene to give 4′-MPP. A conversion of 62% of priopionic anyhydride is obtained after 3 h, with 100% mono-acylated product containing 67% 4′-MPP. Water is the only co-product of the overall reaction. A suitable kinetic model was developed. The reactions were carried out without using any solvent in order to make the process cleaner and greener.
Yadav, Ganapati D.,Kamble, Shashikant B.
experimental part
p. 265 - 274
(2012/08/28)

A facile synthesis of α-fluoro ketones catalyzed by [Cp*IrCl2]2
Allylic alcohols are isomerized into enolates (enols) by [Cp*IrCl2]2. The enolates react with Selectfluor present in the reaction media. This method produces α-fluoro ketones as single constitutional isomers in high yields. Georg Thieme Verlag Stuttgart. New York.
Ahlsten, Nanna,Bartoszewicz, Agnieszka,Agrawal, Santosh,Martin-Matute, Belen
p. 2600 - 2608
(2011/10/02)

Mobilizing Cu(I) for carbon-carbon bond forming catalysis in the presence of thiolate. Chemical mimicking of metallothioneins
Copper(I) is rendered catalytically viable in the presence of thiolate by the design of a small molecule chemical analogue of the metallothionein system in which an N-O reactant serves the same conceptual purpose of the S-S reactant of the biological system.
Zhang, Zhihui,Lindale, Matthew G.,Liebeskind, Lanny S.
supporting information; experimental part
p. 6403 - 6410
(2011/06/19)

Thermal retro-aldol reaction using fluorous ether F-626 as a reaction medium
A high-boiling, fluorous-organic hybrid ether, F-626, was tested for use in thermal retro-aldol reactions and found to be an excellent reaction medium in view of the ease of separation from the product by fluorous/organic biphasic treatment. The recovered F-626 can be readily reused for subsequent runs.
Fukuyama, Takahide,Kawamoto, Takuji,Okamura, Takahiro,Denichoux, Aurelien,Ryu, Ilhyong
experimental part
p. 2193 - 2196
(2010/10/21)

N, N′-dioxide-Cu(OTf)2 complex catalyzed highly enantioselective amination reaction of N-acetyl enamide
The N,N′-dioxide-Cu(OTf)2 complexes were applied in the asymmetric amination reaction of N-acetyl enamides with dialkyl azodicarboxylate, giving the corresponding products in good yields with high enantioselectivities (up to 91% ee). Precursors of vicinal diamine were readily obtained with excellent diastereoselectivities (>95:5) by NaBH4 reduction.
Chang, Lu,Kuang, Yulong,Qin, Bo,Zhou, Xin,Liu, Xiaohua,Lin, Lili,Feng, Xiaoming
supporting information; scheme or table
p. 2214 - 2217
(2010/08/06)