cas 530-46-1, 4-Fluoro-4'-methylbenzophenone

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Suzuki-Miyaura cross-coupling of esters by selective O-C(O) cleavage mediated by air- And moisture-stable [Pd(NHC)(μ-Cl)Cl]2precatalysts: Catalyst evaluation and mechanism
The cross-coupling of aryl esters has emerged as a powerful platform for the functionalization of otherwise inert acyl C-O bonds in chemical synthesis and catalysis. Herein, we report a combined experimental and computational study on the acyl Suzuki-Miyaura cross-coupling of aryl esters mediated by well-defined, air- and moisture-stable Pd(ii)-NHC precatalysts [Pd(NHC)(μ-Cl)Cl]2. We present a comprehensive evaluation of [Pd(NHC)(μ-Cl)Cl]2 precatalysts and compare them with the present state-of-the-art [(Pd(NHC)allyl] precatalysts bearing allyl-type throw-away ligands. Most importantly, the study reveals [Pd(NHC)(μ-Cl)Cl]2 as the most reactive precatalysts discovered to date in this reactivity manifold. The unique synthetic utility of this unconventional O-C(O) cross-coupling is highlighted in the late-stage functionalization of pharmaceuticals and sequential chemoselective cross-coupling, providing access to valuable ketone products by a catalytic mechanism involving Pd insertion into the aryl ester bond. Furthermore, we present a comprehensive study of the catalytic cycle by DFT methods. Considering the clear advantages of [Pd(NHC)(μ-Cl)Cl]2 precatalysts on several levels, including facile one-pot synthesis, superior atom-economic profile to all other Pd(ii)-NHC catalysts, and versatile reactivity, these should be considered as the 'first-choice' catalysts for all routine applications in ester O-C(O) bond activation.
Cavallo, Luigi,Nolan, Steven P.,Poater, Albert,Szostak, Michal,Yang, Shiyi,Zhou, Tongliang
p. 3189 - 3197
(2021/05/25)

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)

Self-Assembled 2,3-Dicyanopyrazino Phenanthrene Aggregates as a Visible-Light Photocatalyst
In this study, 2,3-dicyanopyrazino phenanthrene (DCPP), a commodity chemical that can be prepared at an industrial scale, was used as a photocatalyst in lieu of Ru or Ir complexes in C-X (X = C, N, and O) bond-forming reactions under visible-light irradiation. In these reactions, [DCPP]n aggregates were formed in situ through physical π-πstacking of DCPP monomers in organic solvents. These aggregates exhibited excellent photo- and electrochemical properties, including a visible light response (430 nm), long excited-state lifetime (19.3 μs), high excited-state reduction potential (Ered([DCPP]n*/[DCPP]n·-) = +2.10 V vs SCE), and good reduction stability. The applications of [DCPP]n aggregates as a versatile visible-light photocatalyst were demonstrated in decarboxylative C-C cross-coupling, amidation, and esterification reactions.
He, Min,Yu, Xiaoqiang,Wang, Yi,Li, Fei,Bao, Ming
p. 5016 - 5025
(2021/04/12)

Palladium-Catalyzed Amide N-C Hiyama Cross-Coupling: Synthesis of Ketones
N-Acylglutarimides and arylsiloxanes reacted in the presence of Pd(OAc)2/PCy3, Et3N·3HF, and LiOAc to provide the corresponding arylketones in good yields. Aryl-, vinyl-, and alkyl-substituted N-acylglutarimides showed good activity in the coupling reactions of arylsiloxanes. The reaction had a broad substrate scope and showed good functional group tolerance. N-Benzoylsuccinimide and N-protected N-phenylbenzamides showed good activities in coupling reactions with phenylsiloxane. The employment of CuF2 as an activor afforded the decarbonylative products at 160 °C.
Idris, Muhammad Aliyu,Lee, Sunwoo
supporting information
p. 9190 - 9195
(2020/11/18)

Heterogeneous Suzuki-Miyaura coupling of heteroaryl ester: Via chemoselective C(acyl)-O bond activation
A site-selective supported palladium nanoparticle catalyzed Suzuki-Miyaura cross-coupling reaction with heteroaryl esters and arylboronic acids as coupling partners was developed. This methodology provides a heterogeneous catalytic route for aryl ketone formation via C(acyl)-O bond activation of esters by successful suppression of the undesired decarbonylation phenomenon. The catalyst can be reused and shows high activity after eight cycles. The XPS analysis of the catalyst before and after the reaction suggested that the reaction might be performed via a Pd0/PdII catalytic cycle that began with Pd0.
Ma, Hongpeng,Bai, Chaolumen,Bao, Yong-Sheng
p. 17266 - 17272
(2019/06/24)

Ligand-free Palladium-Catalyzed Carbonylative Suzuki Coupling of Aryl Iodides in Aqueous CH3CN with Sub-stoichiometric Amount of Mo(CO)6 as CO Source
A new method for the synthesis of diaryl and heterodiaryl ketones has been established based on the palladium-catalyzed carbonylative Suzuki coupling approach with sub-stoichiometric Mo(CO)6 as CO source. Using 0.5 mol% of Pd(TFA)2 as catalyst, 0.5 equivalent of Mo(CO)6 as solid carbonyl reagent and 3 equivalent of K3PO4 as base, a wide range of functionalized (hetero)aryl iodides and (hetero)aryl boronic acids could smoothly proceed the carbonylative cross-coupling reaction in aqueous CH3CN at 50 °C, affording the corresponding ketones in good to excellent yields. The newly developed method was easy to operate under mild conditions with high efficiency. (Figure presented.).
Sun, Nan,Sun, Qingxia,Zhao, Wei,Jin, Liqun,Hu, Baoxiang,Shen, Zhenlu,Hu, Xinquan
p. 2117 - 2123
(2019/03/28)

Transition-Metal-Free Carbonylative Suzuki-Miyaura Reactions of Aryl Iodides with Arylboronic Acids Using N-Formylsaccharin as CO Surrogate
Unprecedented, high yielding, transition-metal-free carbonylative Suzuki-Miyaura reactions of aryl iodides with arylboronic acids using N-formylsaccharin as CO surrogate have been developed. Notably, this general protocol was adapted to the synthesis of the triglyceride and cholesterol regulator drug, fenofibrate, and carbon-13 labeled biaryl ketone. (Figure presented.).
Yu, Dezhong,Xu, Fangning,Li, Dan,Han, Wei
supporting information
p. 3102 - 3107
(2019/05/21)

Cercosporin-bioinspired selective photooxidation reactions under mild conditions
The development of an efficient system for selective oxidation of organic compounds to generate more valuable compounds with molecular oxygen is a significant challenge in industrial chemistry. Bioinspired by the ability of naturally occurring perylenequinonoid pigments (PQPs) to generate reactive oxygen species (ROS) upon photoirradiation, here we report that cercosporin, one of the perylenequinonoid pigments, can function as a cost-effective and environmentally friendly photocatalyst for a wide range of selective oxidations, including benzylic C-H bonds to carbonyls, amines to aldehydes, and sulfides to sulfoxides. All of the representative reactions proceeded smoothly with high efficiency under mild conditions. Owing to the use of inexpensive metal-free visible light-driven photocatalyst produced from microbial fermentation with cheap glucose as the starting material and the ease of handling, we expect that this developed method will be particularly attractive for many more applications in synthetic transformation.
Li, Jia,Bao, Wenhao,Tang, Zhaocheng,Guo, Baodang,Zhang, Shiwei,Liu, Haili,Huang, Shuping,Zhang, Yan,Rao, Yijian
supporting information
p. 6073 - 6081
(2019/11/20)

Highly efficient synthesis of aryl ketones by PEPPSI-palladium catalyzed acylative Suzuki coupling of amides with diarylborinic acids
An improved acylative cross-coupling of various N-methyl-N-tosyl amides with diarylborinic acids for synthesis of aryl ketones is developed. In most cases, aryl ketones could be obtained in excellent yields by using 1 mol% 2,6-diisopropylphenylimidazolylidene and 3-chloropyridine co-supported palladium chloride as catalyst in the presence of 3 equiv. K2CO3 as base in refluxing THF. The readily prepared and cost-effective substrates, N-methyl-N-tosylamides and diarylborinic acids, and the commercially available catalyst system promise a practical and efficient access to aryl ketones.
Wang, Chen,Huang, Lingyun,Wang, Fengze,Zou, Gang
supporting information
p. 2299 - 2301
(2018/05/16)

A general approach to intermolecular carbonylation of arene C-H bonds to ketones through catalytic aroyl triflate formation
The development of metal-catalysed methods to functionalize inert C-H bonds has become a dominant research theme in the past decade as an approach to efficient synthesis. However, the incorporation of carbon monoxide into such reactions to form valuable ketones has to date proved a challenge, despite its potential as a straightforward and green alternative to Friedel-Crafts reactions. Here we describe a new approach to palladium-catalysed C-H bond functionalization in which carbon monoxide is used to drive the generation of high-energy electrophiles. This offers a method to couple the useful features of metal-catalysed C-H functionalization (stable and available reagents) and electrophilic acylations (broad scope and selectivity), and synthesize ketones simply from aryl iodides, CO and arenes. Notably, the reaction proceeds in an intermolecular fashion, without directing groups and at very low palladium-catalyst loadings. Mechanistic studies show that the reaction proceeds through the catalytic build-up of potent aroyl triflate electrophiles.
Kinney, R. Garrison,Tjutrins, Jevgenijs,Torres, Gerardo M.,Liu, Nina Jiabao,Kulkarni, Omkar,Arndtsen, Bruce A.
p. 193 - 199
(2018/02/06)

Integrative Photoreduction of CO2 with Subsequent Carbonylation: Photocatalysis for Reductive Functionalization of CO2
Efficient conversion of CO2 into fuels and chemicals with solar energy would be promising, but also faces great challenge. In this context, we describe the photoreductive functionalization of CO2 to construct new C?C, C?N, and C?O bonds through the respective Pd-catalyzed Suzuki carbonylation, aminocarbonylation, and alkoxycarbonylation of aryl iodides with CO in situ generated through the photoreduction of CO2. This protocol opens up an alternative avenue for CO2 utilization by harnessing solar energy.
He, Xing,Cao, Yu,Lang, Xian-Dong,Wang, Ning,He, Liang-Nian
p. 3382 - 3387
(2018/09/14)

At normal pressure fragrant ketone copper catalytic synthesis method
The invention discloses a method of synthesizing diaryl ketone under normal pressure by virtue of copper catalysis. The method is as follows: in a solvent alcohol or aqueous liquor of alcohol, under action of alkali and acid, adding a copper catalyst, alkyl iodide, alkyl boric acid and carbon monoxide to directly carry out crossed coupling reaction to prepare diaryl ketone compounds. According to the invention, the method of preparing diaryl ketone compounds by carbonylation Suzuki coupling reaction has the advantages as follows: the catalyst is wide in source, cheap and small in toxicity; the reaction is free of ligand in reaction and good in activity; the reaction is carried out under the normal pressure and selectivity is high; a substrate source is wide and stable; functional group compatibility is good and scope of application for the substrate is wide; a reaction medium is environment-friendly and recyclable. Under the condition of optimizing reaction conditions, the target product separating yield is 95%.
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Paragraph 0032; 0033; 0038

(2017/07/14)

Experimental Evaluation of (L)Au Electron-Donor Ability in Cationic Gold Carbene Complexes
29Si NMR spectroscopy was employed to evaluate the electron donor properties of the (L)Au fragments in the cationic gold (β,β-disilyl)vinylidene complexes [(L)Au=C=CSi(Me)2CH2CH2Si(Me)2]+B(C6F5)4? [L=P(tBu)2o-biphenyl or NHC] relative to the p-substituted aryl group in the α-aryl-(β,β-disilyl)vinyl cations [(p-C6H4X)-C= CSi(Me)2CH2CH2Si(Me)2]+B(C6F5)4?. Similarly, 19F NMR was employed to evaluate the σ- and π-electron donor properties of the (L)Au fragments in the neutral gold fluorophenyl complexes (L)Au(C6H4F) and in the cationic (fluorophenyl)methoxycarbene complexes [(L)AuC(OMe)(C6H4F)]+SbF6? [L=P(tBu)2o-biphenyl or IPr] relative to the p-substituted aryl group of the protonated monofluorobenzophenones [(p-C6H4X)(C6H4F)COH]+OTf?. The results of these studies indicate that relative to p-substituted aryl groups, the gold (L)Au fragments [L=P(tBu)2o-biphenyl or NHC] are significantly more inductively electron donating and are comparable π-donors and for this reason, the extent of (L)Au→C1 electron donation in gold carbene complexes appears to exceed that provided by a p-(dimethyamino)phenyl group. Furthermore, the [L=P(tBu)2o-biphenyl]Au fragment is a nominally stronger electron donor than the (IPr)Au fragment, and both are significantly more inductively electron donating than the (PPh3)Au and [P(OMe)3]Au fragments.
Carden, Robert G.,Lam, Nathan,Widenhoefer, Ross A.
supporting information
p. 17992 - 18001
(2017/11/27)

Reactions catalyzed by a binuclear copper complex: Selective oxidation of alkenes to carbonyls with O2
Terminal alkenes were selectively cleaved into ketones and aldehydes catalyzed by a binuclear copper catalyst bearing a simple salicylate ligand with O2 as the oxidant. The reaction was carried out under an atmosphere of O2 (balloon) with 0.5 mol% of catalyst and could be performed on a gram scale, providing a convenient and practical method for the cleavage of terminal alkenes into carbonyl compounds.
Liu, Yuxia,Xue, Dong,Li, Chaoqun,Xiao, Jianliang,Wang, Chao
p. 5510 - 5514
(2017/12/08)

Pd/C in Propylene Carbonate: A Sustainable Catalyst–Solvent System for the Carbonylative Suzuki–Miyaura Cross-Coupling Using N-Formylsaccharin as a CO Surrogate
This work documents the first Pd/C-catalyzed carbonylative Suzuki–Miyaura cross-coupling of aryl iodides with N-formylsaccharin as a CO surrogate. In contrast to previous reaction protocols, which make use of toxic and hazardous solvents, the reaction could be advantageously performed in propylene carbonate as an environmentally benign and sustainable polar aprotic solvent. A range of biaryl ketones, including (4-methoxyphenyl)(3,4,5-trimethoxyphenyl)methanone, an antineoplastic belonging to the phenstatin family, could be synthesized under cocatalyst-free, additive-free and ligand-free conditions. The Pd/C could be recycled up to five times under CO surrogacy with only a marginal decrease in catalytic activity. The reaction could also be scaled up to gram-scale syntheses.
Gautam, Prashant,Gupta, Rashi,Bhanage, Bhalchandra M.
p. 3431 - 3437
(2017/07/04)

Palladium-Catalyzed Denitrogenative Synthesis of Aryl Ketones from Arylhydrazines and Nitriles Using O2 as Sole Oxidant
An efficient and simple palladium-catalyzed approach for the synthesis of aryl ketones from low-cost nitriles and arylhydrazines using molecular oxygen (O2) as sole oxidant via C-N bond cleavage is reported. Various aryl ketones were synthesized in moderate to good yields under mild conditions. A possible mechanism involving the PdII/Pd0 catalytic cycle process is depicted, and a cationic palladium intermediate was detected by ESI-MS.
Wang, Xu,Huang, Yubing,Xu, Yanli,Tang, Xiaodong,Wu, Wanqing,Jiang, Huanfeng
p. 2211 - 2218
(2017/02/26)

Ni-Catalyzed Reductive Cross-Coupling of Amides with Aryl Iodide Electrophiles via C-N Bond Activation
A Ni-catalyzed reductive cross-coupling reaction between two electrophiles, amides and aryl iodides, has been developed. This work is the first example using amide as an electrophile to couple with another electrophile, instead of using highly basic and pyrophoric nucleophiles. Furthermore, the Ni catalyst chemoselectively inserting the C-N bond of amide triggered the reductive cross-coupling reaction, which solves the problem that the Ni catalyst preferentially inserts the more reactive C-I bond to form a self-coupling product.
Ni, Shengyang,Zhang, Wenzhong,Mei, Haibo,Han, Jianlin,Pan, Yi
p. 2536 - 2539
(2017/05/24)

At normal pressure fragrant ketone nickel catalytic synthesis method
The invention discloses a method for synthesizing diarylketone under the catalysis of nickel at normal pressure. The method comprises the steps of enabling aryl iodide, arylboronic acid and carbon monoxide to be subjected to direct cross-coupling reaction in a solvent polyethylene glycol or a water solution of polyethylene glycol under the catalysis of a nickel catalyst and the combined action of alkaline and acid at normal pressure to prepare a diarylketone compound. The method has the advantages of wide catalyst source, low price, little toxicity, reaction at normal pressure, high selectivity, no need of ligands in reaction, good activity, good functional group compatibility, wide substrate application range, wide substrate source, stable substrate, green and recyclable reaction medium and the like. The separation yield of target products is up to 93% under an optimized reaction condition.
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Paragraph 0003; 0017; 0027-0033

(2017/08/02)

Transition metal-free Suzuki type cross-coupling reaction for the synthesis of dissymmetric ketones
A simple, efficient and metal-free route for the synthesis of dissymmetric ketones through Suzuki type cross-coupling reaction has been established. This strategy signifies an attractive, cost-effective and operationally convenient tool for the synthesis of a wide range of dissymmetric ketones. Although conventional routes for the synthesis of ketones have been widely used, the potential challenge with these methods is functional group tolerance. The reported metal-free method represents a reaction with moderate functional group tolerance. The procedure is operationally convenient and shows broad substrate scope with good to excellent product yields.
Jadhav, Sanjay,Rashinkar, Gajanan,Salunkhe, Rajashri,Kumbhar, Arjun
supporting information
p. 3201 - 3204
(2017/07/27)

A 4-methyl -4 the [...] -fluoro-benzophenone preparation method (by machine translation)
The invention belongs to the technical field of fine chemicals, in particular to a 4 the [...] methyl -4 the [...] -fluoro-benzophenone preparation method, comprising the following steps: in a reaction flask by adding P-benzoic acid, the methyl boric acid, and adding nickel chloride, zinc powder, luen pyridine as the catalyst of the catalytic system, then adding a proper amount of potassium carbonate as alkali and right amount of magnesium chloride as an additive, equivalent Boc-anhydride and, finally adding amount of tetrahydrofuran as a solvent, the reaction at room temperature the 15 [...] 24h, separating the 4 [...] methyl -4 the [...] -fluoro-benzophenone; the invention compared with the prior art, provides a green, the production cost is low, the operation is convenient, mild reaction conditions and high safety of the 4 [...] methyl -4 the [...] -fluoro-benzophenone preparation method, and the raw material is cheap and easy to obtain, mild reaction conditions, the operation is simple, has good prospects for development, with a potential prospects for industrial application, is worth of popularization and application. (by machine translation)
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Paragraph 0022; 0023

(2018/02/04)

Iron-catalyzed carbonylation of aryl halides with arylborons using stoichiometric chloroform as the carbon monoxide source
A general iron-catalyzed carbonylative Suzuki-Miyaura coupling of aryl halides with arylborons is reported, using stoichiometric CHCl3 as the CO source. The high efficiency, economy, selectivity, and operational simplicity of this transformation make this method a valuable tool in organic synthesis. Importantly, the presented strategy allows effective 13C labeling simply by using the commercially available 13C-labeled CHCl3. On the basis of the initial mechanistic exploration, an aryl radical intermediate is proposed in the present carbonylation process.
Zhao, Hongyuan,Du, Hongyan,Yuan, Xiaorong,Wang, Tianjiao,Han, Wei
supporting information
p. 5782 - 5787
(2016/11/06)

Efficient Synthesis of Diaryl Ketones by Nickel-Catalyzed Negishi Cross-Coupling of Amides by Carbon–Nitrogen Bond Cleavage at Room Temperature Accelerated by a Solvent Effect
The first Negishi cross-coupling of amides for the synthesis of versatile diaryl ketones by selective C?N bond activation under exceedingly mild conditions is reported. The cross-coupling was accomplished with bench-stable, inexpensive precatalyst [Ni(PPh3)2Cl2] that shows high functional-group tolerance and enables the synthesis of highly functionalized diaryl ketone motifs. The coupling occurred with excellent chemoselectivity favoring the ketone (cf. biaryl) products. Notably, this process represents the mildest conditions for amide N?C bond activation accomplished to date (room temperature, 10 min). Considering the versatile role of polyfunctional biaryl ketone linchpins in modern organic synthesis, availability, and excellent functional-group tolerance of organozinc reagents, this strategy provides a new platform for amide N?C bond/organozinc cross-coupling under mild conditions.
Shi, Shicheng,Szostak, Michal
p. 10420 - 10424
(2016/07/21)

Palladium-Catalyzed Room-Temperature Acylative Suzuki Coupling of High-Order Aryl Borons with Carboxylic Acids
This note describes a dimethyl dicarbonate-assisted, Pd(OAc)2/PPh3-catalyzed acylative Suzuki coupling of carboxylic acids with diarylborinic acids or tetraarylboronates for practical and efficient synthesis of sterically undemanding aryl ketones at room temperature. More than just cost-effective alternatives to aryl boronic acids, diarylborinic acids and tetraarylboronates displayed higher reactivity in the acylative Suzuki coupling. A variety of alkyl aryl ketones, including those bearing a hydroxy, bromo, or carbonyl group, could be readily obtained in modest to excellent yields.
Si, Shufen,Wang, Chen,Zhang, Nan,Zou, Gang
p. 4364 - 4370
(2016/06/09)

A versatile approach for the synthesis of para -substituted arenes via palladium-catalyzed C-H functionalization and protodecarboxylation of benzoic acids
While a great number of ortho C-H functionalization reactions have been developed and several breakthroughs have been achieved in meta C-H activation, para C-H functionalization is still in its infancy stage. In this article, a versatile strategy for the synthesis of para-substituted arenes has been developed via a tandem process consisting of palladium-catalyzed C-H functionalization and subsequent copper-catalyzed protodecarboxylation of benzoic acids. Both electron-withdrawing and electron-donating functionalities can be introduced into the para positions of arenes bearing a variety of substituents.
Pan, Shulei,Zhou, Bo,Zhang, Yanghui,Shao, Changdong,Shi, Guangfa
supporting information
p. 277 - 281
(2016/01/20)

Merging Photoredox and Nickel Catalysis: The Direct Synthesis of Ketones by the Decarboxylative Arylation of α-Oxo Acids
The direct decarboxylative arylation of α-oxo acids has been achieved by synergistic visible-light-mediated photoredox and nickel catalysis. This method offers rapid entry to aryl and alkyl ketone architectures from simple α-oxo acid precursors via an acyl radical intermediate. Significant substrate scope is observed with respect to both the oxo acid and arene coupling partners. This mild decarboxylative arylation can also be utilized to efficiently access medicinal agents, as demonstrated by the rapid synthesis of fenofibrate. The direct decarboxylative arylation of α-oxo acids has been achieved by synergistic visible-light-mediated photoredox and nickel catalysis. This method offers rapid entry to aryl and alkyl ketone architectures from simple α-oxo acid precursors via an acyl radical intermediate. Significant substrate scope is observed with respect to both the oxo acid and arene coupling partners.
Chu, Lingling,Lipshultz, Jeffrey M.,Macmillan, David W. C.
supporting information
p. 7929 - 7933
(2015/06/30)

Palladium-catalyzed acylative cross-coupling of amides with diarylborinic acids and sodium tetraarylborates
Abstract A general and efficient acylative Suzuki coupling of active amides with diarylborinic acids has been achieved by using 1 mol% Pd(PCy3)2Cl2/0.6 mol% PCy3 as catalyst system taking advantage of modifiable reactivities of acyl-nitrogen bonds of amides. Both electronic and steric influences from either aryl or acyl counterparts on the coupling proved to be negligible or small. A variety of aryl ketones including sterically hindered ones could be synthesized by the coupling of diarylborinic acids in good to excellent yields. Sodium tetraarylborates could also be used as high atom-economy aryl source in the palladium-catalyzed cross-coupling with active amides.
Li, Xijing,Zou, Gang
p. 136 - 145
(2015/07/27)

Metal-free efficient cross coupling of aromatic aldehydes with aryldiazonium tetrafluoroborates using DTBP as a radical initiator
A highly efficient, metal-free, one-pot radical route to access diaryl ketones from aromatic aldehydes is reported. The protocol renders cross coupling of aromatic aldehydes with aryl diazonium tetrafluoroborates using inexpensive di-tert-butylperoxide (DTBP) as a radical initiator under mild conditions. The reaction offers a convenient alternative to the Friedel-Crafts acylation for the synthesis of diaryl ketones.
Tripathi, Shubhangi,Singh, Sachchida N.,Yadav, Lal Dhar S.
supporting information
p. 4211 - 4214
(2015/06/22)

An efficient and recyclable thermoregulated phosphine-palladium catalyst for the carbonylative Suzuki coupling of aryl halides with arylboronic acids in water
An efficient protocol has been developed for the carbonylative Suzuki coupling of aryl halides using the thermoregulated phosphine-palladium as a reusable catalyst in pure water. This protocol was applied to a wide variety of hindered and functionalized aryl iodides and bromides with arylboronic acids, to afford the desired biaryl ketones in good to high yields. The palladium catalyst was easily recovered in the aqueous phase and reused up to eight cycles without a significant decrease in its activity.
Hao, Yuanping,Jiang, Jingyang,Wang, Yanhua,Jin, Zilin
p. 106 - 110
(2015/09/28)

Simple preparation of aryltributylstannanes and its application to one-pot synthesis of diaryl ketones
Transfer of aryl group from boron to tin can be achieved by simple treatment of arylboronic acids with tributyltin methoxide at 100 °C for 1 h under neat conditions. The resulting aryltributylstannanes are applicable to one-pot synthesis of diaryl ketones. Thus, Pd-catalyzed cross-coupling reaction with aroyl chlorides is allowed to proceed without isolation step to produce the corresponding diaryl ketones in good to high yields.
Oikawa, Asuka,Kindaichi, Gan,Shimotori, Yasutaka,Okimoto, Mitsuhiro,Hoshi, Masayuki
supporting information
p. 1705 - 1711
(2015/03/30)

Nickel-catalyzed cross-coupling of carboxylic anhydrides with arylboronic acids
A nickel-based catalyst was employed in the cross-coupling of carboxylic anhydrides with arylboronic acids, and the reaction was carried out under mild conditions. This new protocol provides an efficient, cheap and convenient alternative to synthesizing aromatic ketones.
Chen, Qiang,Fan, Xin-Heng,Zhang, Li-Peng,Yang, Lian-Ming
p. 53885 - 53890
(2015/01/16)

In situ generated nickel nanoparticle-catalyzed carbonylative Suzuki reactions of aryl iodides with arylboronic acids at ambient CO pressure in poly(ethylene glycol)
A general in situ generated nickel nanoparticle-catalyzed carbonylative Suzuki reactions of aryl iodides with arylboronic acids at atmospheric CO pressure in poly(ethylene glycol) has been demonstrated. A wide range of aryl iodides and arylboronic acids can be coupled to the corresponding biarylketones with high yields even in the absence of an added ligand and at low catalyst loading. The nature of the active catalytic species is discussed. This journal is
Zhong, Yanzhen,Gong, Xinxing,Zhu, Xiaoshu,Ni, Zhuchao,Wang, Haoyang,Fu, Jinglin,Han, Wei
p. 63216 - 63220
(2015/02/19)

Iron-catalyzed carbonylative Suzuki reactions under atmospheric pressure of carbon monoxide
The first highly effective iron-catalyzed carbonylative Suzuki reaction has been developed. Substrates with electron-donating or electron-withdrawing functionality, ortho-substitution, as well as active groups proceeded smoothly, affording desired products in high yields. This protocol is economical, environmentally benign and practical for the synthesis of biaryl ketones. This journal is the Partner Organisations 2014.
Zhong, Yanzhen,Han, Wei
supporting information
p. 3874 - 3877
(2014/04/03)

Copper-catalyzed carbonylative Suzuki coupling of aryl iodides with arylboronic acids under ambient pressure of carbon monoxide
An efficient and ligandless nanocopper-catalyzed carbonylative cross-coupling of aryl iodides with arylboronic acids at ambient CO pressure in poly(ethylene glycol), has been developed. This protocol is general, practical, and recyclable, and offers an attractive alternative to the corresponding palladium-mediated carbonylative Suzuki process for the construction of biaryl ketone scaffolds.
Cheng, Laijin,Zhong, Yanzhen,Ni, Zhuchao,Du, Hongyan,Jin, Fengli,Rong, Qi,Han, Wei
p. 44312 - 44316
(2014/12/10)

In situ generation of palladium nanoparticles: Ligand-free palladium catalyzed pivalic acid assisted carbonylative Suzuki reactions at ambient conditions
Highly selective carbonylative Suzuki reactions of aryl iodides with arylboronic acids using an in situ generated nanopalladium system furnished products in high yields. The reactions were performed under ambient conditions and in the absence of an added ligand. The key to success is the addition of pivalic acid, which can effectively suppress undesired Suzuki coupling. The synthesis can be easily scaled up, and the catalytic system can be reused up to nine times. The nature of the active catalytic species are discussed.
Zhou, Qing,Wei, Shaohua,Han, Wei
p. 1454 - 1460
(2014/03/21)

NHC-Pd(II)-Im (NHC=N-heterocyclic carbene, Im=1-methylimidazole) complex catalyzed coupling reaction of arylboronic acids with carboxylic acid anhydrides in water
A well-defined N-heterocyclic carbene (NHC)-palladium chloride-imidazole complex exhibited high catalytic activity in the coupling reaction of arylboronic acids with carboxylic acid anhydrides in pure water under mild conditions. Under the optimal conditions, all reactions gave the desired coupling products in moderate to high yields.
Lin, Xiao-Fang,Li, Yao,Li, Shuang-Yan,Xiao, Zheng-Kang,Lu, Jian-Mei
experimental part
p. 5806 - 5809
(2012/09/08)

Synthesis of fluorenone derivatives through Pd-catalyzed dehydrogenative cyclization
Palladium-catalyzed dual C-H functionalization of benzophenones to form fluorenones by oxidative dehydrogenative cyclization is reported. This method provides a concise and effective route toward the synthesis of fluorenone derivatives, which shows outstanding functional group compatibility.
Li, Hu,Zhu, Ru-Yi,Shi, Wen-Juan,He, Ke-Han,Shi, Zhang-Jie
supporting information
p. 4850 - 4853,4
(2012/12/12)

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
experimental part
p. 1436 - 1442
(2012/03/09)

Practical one-pot preparation of ketones from aryl and alkyl bromides with aldehydes and DIH via Grignard reagents
Various diaryl ketones, alkyl aryl ketones, and dialkyl ketones were efficiently prepared in good yields by the reactions of the Grignard reagents derived from aryl or alkyl bromides, followed by the reactions with aromatic or aliphatic aldehydes and the subsequent treatment with 1,3-diiodo-5,5- dimethylhydantoin and K2CO3, in a one-pot method. The same treatment of aromatic bromides bearing electron-withdrawing groups, such as ester, nitrile, ketone, and nitro groups with i-PrMgCl·LiCl or PhMgCl instead of Mg, also provided the corresponding diaryl and alkyl aryl ketones in good yields. The above methods are simple and practical transition-metal-free methods for the preparation of various diaryl ketones and alkyl aryl ketones bearing electron-rich aromatic groups and electron-deficient aromatic groups, as well as dialkyl ketones.
Dohi, Souya,Moriyama, Katsuhiko,Togo, Hideo
experimental part
p. 6557 - 6564
(2012/08/27)

Direct synthesis of aryl ketones by palladium-catalyzed desulfinative addition of sodium sulfinates to nitriles
Mild yet direct: A convenient and efficient method for the synthesis of various aryl ketones by palladium-catalyzed desulfinative addition of aromatic sulfinic acid sodium salts to various nitriles is described (see scheme). Aromatic and aliphatic nitriles are successfully reacted with arenesulfinic acid sodium salts to form aryl ketones in good yields.
Liu, Jing,Zhou, Xianya,Rao, Honghua,Xiao, Fuhong,Li, Chao-Jun,Deng, Guo-Jun
supporting information; experimental part
p. 7996 - 7999
(2011/08/22)

Ionically tagged benzimidazole palladium(II) complex: Preparation and catalytic application in cross-coupling reactions
An imidazolium chloride tagged palladium(II) complex has been conveniently prepared and structurally analyzed. It is active toward cross-coupling of arylboronic acid with aryl halide and benzoyl chloride, giving moderate to high yield of the desired biaryls and aryl ketones, respectively. The present phosphine-free (N-N)Pd(II) complex could be efficiently recycled at least four times with minor decrease of activity in the aqueous Suzuki-Miyaura coupling reaction.
Zhang, Li,Wu, Junliang,Shi, Lijun,Xia, Chungu,Li, Fuwei
supporting information; experimental part
p. 3897 - 3901
(2011/08/09)

"Greener" Friedel-Crafts acylations: A metal- and halogen-free methodology
Chemical equations presented. The utility of methanesulfonic anhydride for promoting the Friedel-Crafts acylation reaction of aryl and alkyl carboxylic acids is disclosed. This reagent allows the preparation of aryl ketones in good yield with minimal waste containing no metallic or halogenated components, clearly differentiating it from other available methodologies.
Wilkinson, Mark C.
supporting information; experimental part
p. 2232 - 2235
(2011/06/24)

Copper-catalyzed arylation of arylboronic acids with aldehydes
A novel copper-catalyzed arylation of arylboronic acids with aldehydes under oxygen atmosphere was achieved in the presence of Cu(OTf)2 and Xantphos, affording diaryl ketone derivatives in moderate to good yields. The efficiency of this reaction was demonstrated by the compatibility with fluoro, bromo, chloro, nitro, -methylsulfonyl, and trifluoromethyl groups. Georg Thieme Verlag Stuttgart ? New York.
Zheng, Hanmei,Ding, Jinchang,Chen, Jiuxi,Liu, Miaochang,Gao, Wenxia,Wu, Huayue
experimental part
p. 1626 - 1630
(2011/08/03)

Atom-efficient cross-coupling reactions of triarylbismuths with acyl chlorides under Pd(0) catalysis
The atom-efficient cross-coupling reaction of triarylbismuths with a variety of aliphatic, aromatic, and hetero-aromatic acyl chlorides was demonstrated to afford high yields of cross-coupled ketones under palladium catalysis. The corresponding cross-coupling reaction with diacid chlorides also furnished bis-coupled ketones in good yields.
Rao, Maddali L.N.,Venkatesh, Varadhachari,Banerjee, Debasis
p. 12917 - 12926
(2008/03/28)

An atom-efficient palladium-catalyzed cross-coupling reaction of triarylbismuths with acid chlorides: synthesis of diaryl and alkyl aryl ketones
The cross-coupling reaction of triarylbismuths with acid chlorides using a catalytic amount of PdCl2/PPh3 afforded the corresponding ketones in high yields. The reactions of aromatic and aliphatic acid chlorides occurred with atom efficiency, as 3 equiv of acid chlorides coupled effectively with 1 equiv of triarylbismuths to yield 3 equiv of the corresponding diaryl and alkyl aryl ketones.
Rao, Maddali L.N.,Venkatesh, Varadhachari,Jadhav, Deepak N.
p. 6975 - 6978
(2007/10/03)

Palladium-catalyzed coupling of thiol esters with aryl and primary and secondary alkyl organoindium reagents
Thiol esters and organoindium reagents undergo palladium-catalyzed cross-coupling under mild conditions to give ketones in moderate to excellent yields. Aryl and primary/ secondary alkyl organoindium reagents can be used as coupling partners. This method has two advantages over the cross-coupling of thiol esters with boron and tin reagents: (1) no added copper reagent is required to mediate the reaction and (2) for the case of alkyl transfer, no added base is required to activate organoindium reagents for cross-coupling as is required for the coupling of alkyl boron reagents with thiol esters.
Fausett, Bryan W.,Liebeskind, Lanny S.
p. 4851 - 4853
(2007/10/03)

Rh(1,3-bis(2,4,6-trimethylphenyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene) (COD) tetrafluoroborate, an unsymmetrical Rh-homoazallylcarbene: Synthesis, X-ray structure and reactivity in carbonyl arylation and hydrosilylation reactions
The synthesis of novel Rh(1,3-bis(2,4,6-trimethylphenyl)-3,4,5,6- tetrahydropyrimidin-2-ylidene)(COD) tetrafluoroborate (1, COD = η4-1,5-cyclooctadiene) is described. The N-heterocyclic carbene acts as a bidentate ligand with the carbene coordinating to the Rh(I) center and an arene group acting as a homoazallyl ligand. 1 was used in various carbonyl arylation and hydrosilylation reactions allowing the formation of the desired products with unprecedented selectivity and efficiency. Thus, turn-over numbers (TONs) up to 2000 were achieved.
Imlinger, Nicolas,Wurst, Klaus,Buchmeiser, Michael R.
p. 4433 - 4440
(2007/10/03)

Arylation of carbonyl compounds catalyzed by rhodium and iridium 1,3-R 2-tetrahydropyrimidin-2-ylidenes: Structure-reactivity correlations
Six different well-defined rhodium and iridium N-heterocyclic carbene complexes, i.e., RhCl-(1,3-dimesityltetrahydropyrimidin-2-ylidene)(COD) (1), RhBr(1,3-dimesityltetrahydropyrimidin-2-ylidene)-(COD) (2), RhCl[1,3-di(2- propyl)tetrahydropyrimidin-2-ylidene](COD) (3), IrCl(1,3- dimesityltetrahydropyrimidin-2-ylidene)(COD) (4), Rh(CF3COO) (1,3-dimesityltetrahydropyrimidin-2-ylidene)(COD) (5), and IrBr[1,3-di(2-propyl) tetrahydropyrimidin-2-ylidene](COD) (6) (COD = 1,5-cyclooctadiene, mesityl = 2,4,6-trimethylphenyl) have been used as catalysts for the arylation of aldehydes and α,β-unsaturated ketones using different arylboronic acids. Compounds 1-4 and 6 were prepared by reaction of [RhCl(COD)]2 and [IrCl(COD)]2, respectively, with a base and the corresponding 1,3-R2-tetrahydropyrimidinium salt. Compound 5 was prepared by reaction of 1.0 equivalents of CF3COOAg with 1. The use of an excess of CF3COOAg resulted in the replacement of Rh(I) by Ag(I) and yielded Ag(1,3-dimesityltetrahydropyrimidin-2-ylidene)+Rh 2(CF3COO)3(COD)- (8). Compounds 4 and 8 were characterized by X-ray analysis. The activity of the rhodium complexes increased in the order 5 > 3 > 1 > 2, indicating the necessity of strongly electron-withdrawing groups at the metal centers, thus increasing their nucleophilicity. In due consequence, the softer iridium complexes 4 and 6 exhibited significantly reduced catalytic activity albeit with enhanced selectivity. The syntheses of the metal complexes as well as a detailed study on their reactivity in the arylation of carbonyl compounds using equimolar amounts of arylboronic acid and carbonyl compound in the presence of 0.08-1 mol % catalyst are presented.
Imlinger, Nicolas,Mayr, Monika,Wang, Dongren,Wurst, Klaus,Buchmeiser, Michael R.
p. 1836 - 1843
(2007/10/03)

Preparation process of fluorine substituted aromatic compound
A preparation process of a fluorine substituted aromatic compound comprising reacting an alkali metal or alkali earth metal salt of an aromatic compound having a hydroxy group with an organic fluorinating agent is disclosed. As a representative fluorinating agent, a bis-dialkylamino-difluoromethane compound, for example, 2,2′-difluoro-1,3-dimethylimidazolidine, is exemplified. According to the process, an industrially useful fluorinated aromatic compound, for example, a fluorobenzene, a fluorine substituted benzophenone, a fluorine substituted diarylsulfone can be prepared with ease in economy without specific equipment.
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(2008/06/13)

Benzophenone hydrazone derivatives as insecticides
Novel benzophenonehydrazone derivatives represented by the formula (I): wherein, R1 is halogen; R2 is hydrogen or C1-4 alkyl; R3 is cyano, optically substituted C1-4 alkyl, C2-4 alkenyl, C3-4 alkynyl, C1-4 alkyl-carbonyl or C1-4 alkoxy-thiocarbonyl; R4 is hydrogen, phenyl, optionally substituted C1-6 alkyl, optionally substituted C2-8 alkenyl, -CO-R8, -CO-O-R9 or R5 is hydrogen, formyl, phenyl, optionally substituted C1-8 alkyl, optionally substituted C2-8 alkenyl, optionally substituted C3-8 alkynyl, optionally substituted C1-8 alkyl-arbonyl, optionally substituted C1-6 alkyl-oxalyl, optionally substituted C1-8 alkoxy-carbonyl, optionally substituted C1-8 alkoxy-oxalyl, optionally substituted C3-8 cycloalkyl-carbonyl, optionally substituted C2-8 alkenyl-carbonyl or optionally substituted benzoyl; R6 is hydrogen or halogen; R7 is hydrogen, halogen or C1-2 alkyl, C1-4 alkyl-carbonyl or C1-4 alkoxy-thiocarbonyl; n is 0, 1 or 2, provided that n is 0 when R3 is cyano, C1-4 alkyl-carbonyl or C1-4 alkoxy-thiocarbonyl, +Z is a single bond of Anti form or of Syn form. The benzophenonehydrazone derivatives of the formula (I) have excellent insecticidal activities.
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(2008/06/13)