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Evaluation of Cyclic Amides as Activating Groups in N-C Bond Cross-Coupling: Discovery of N-Acyl-δ-valerolactams as Effective Twisted Amide Precursors for Cross-Coupling Reactions
The development of efficient methods for facilitating N-C(O) bond activation in amides is an important objective in organic synthesis that permits the manipulation of the traditionally unreactive amide bonds. Herein, we report a comparative evaluation of a series of cyclic amides as activating groups in amide N-C(O) bond cross-coupling. Evaluation of N-acyl-imides, N-acyl-lactams, and N-acyl-oxazolidinones bearing five- and six-membered rings using Pd(II)-NHC and Pd-phosphine systems reveals the relative reactivity order of N-activating groups in Suzuki-Miyaura cross-coupling. The reactivity of activated phenolic esters and thioesters is evaluated for comparison in O-C(O) and S-C(O) cross-coupling under the same reaction conditions. Most notably, the study reveals N-acyl-δ-valerolactams as a highly effective class of mono-N-acyl-activated amide precursors in cross-coupling. The X-ray structure of the model N-acyl-δ-valerolactam is characterized by an additive Winkler-Dunitz distortion parameter ?(τ+χN) of 54.0°, placing this amide in a medium distortion range of twisted amides. Computational studies provide insight into the structural and energetic parameters of the amide bond, including amidic resonance, N/O-protonation aptitude, and the rotational barrier around the N-C(O) axis. This class of N-acyl-lactams will be a valuable addition to the growing portfolio of amide electrophiles for cross-coupling reactions by acyl-metal intermediates.
Bisz, Elwira,Chen, Hao,Dziuk, B?a?ej,Ejsmont, Krzysztof,Lalancette, Roger,Pyle, Daniel J.,Rahman, Md. Mahbubur,Szostak, Michal,Szostak, Roman,Wang, Qi
p. 10455 - 10466
(2021/07/31)

Pd-Catalysed carbonylative Suzuki-Miyaura cross-couplings using Fe(CO)5under mild conditions: generation of a highly active, recyclable and scalable ‘Pd-Fe’ nanocatalyst
The dual function and role of iron(0) pentacarbonyl [Fe(CO)5] has been identified in gaseous CO-free carbonylative Suzuki-Miyaura cross-couplings, in which Fe(CO)5supplied COin situ, leading to the propagation of catalytically active Pd-Fe nanoparticles. Compared with typical carbonylative reaction conditions, CO gas (at high pressures), specialised exogenous ligands and inert reaction conditions were avoided. Our developed reaction conditions are mild, do not require specialised CO high pressure equipment, and exhibit wide functional group tolerance, giving a library of biaryl ketones in good yields.
Zhu, Zhuangli,Wang, Zhenhua,Jian, Yajun,Sun, Huaming,Zhang, Guofang,Lynam, Jason M.,McElroy, C. Robert,Burden, Thomas J.,Inight, Rebecca L.,Fairlamb, Ian J. S.,Zhang, Weiqiang,Gao, Ziwei
supporting information
p. 920 - 926
(2021/02/09)

Iodine Promoted Conversion of Esters to Nitriles and Ketones under Metal-Free Conditions
We report a novel strategy to prepare valuable nitriles and ketones through the conversion of esters under metal-free conditions. By using the I2/PCl3 system, various substrates including aliphatic and aromatic esters could react with acetonitrile and arenes to afford the desired products in good to excellent yields. This method is compatible with a number of functional groups and provides a simple and practical approach for the synthesis of nitrile compounds and aryl ketones.
Xiao, Jing,Guo, Fengzhe,Li, Yinfeng,Li, Fangshao,Li, Qiang,Tang, Zi-Long
p. 2028 - 2035
(2021/02/03)

Palladium nanoparticles on amino-modified silica-catalyzed C–C bond formation with carbonyl insertion
Abstract: A practical and heterogeneously catalyzed Stille, homo-coupling, and Suzuki carbonylation reaction has been reported using Pd nanoparticles supported on amino-vinyl silica-functionalized magnetic carbon nanotube (CNT@Fe3O4@SiO2-Pd) for the efficient synthesis of symmetrical and unsymmetrical diaryl ketones from aryl iodides. A wide variety of symmetrical and unsymmetrical diaryl ketones were obtained in high yields under CO gas-free conditions using Mo(CO)6 as an efficient carbonyl source. Considering the atom economy of Ph3SnCl, less than an equimolar amount can be applied in Stille transformation, which is of great importance due to the toxicity of organotin derivatives. Moreover, no phosphine ligand and external reducing agent were necessary in these coupling carbonylation reactions. This heterogeneous Pd catalyst offers high activity with very low palladium leaching. Finally, the catalyst can be reused and recycled for six steps without loss in activity, exhibiting good example of sustainable methodology. Graphic abstract: [Figure not available: see fulltext.].
Etemadi-Davan, Elham,Khalili, Dariush,Banazadeh, Ali Reza,Sadri, Ghazal,Arshad, Pourya
p. 1891 - 1903
(2021/02/01)

Visible light-driven direct synthesis of ketones from aldehydes via C[sbnd]H bond activation using NiCu nanoparticles adorned on carbon nano onions
An efficient, straightforward and high yield synthetic approach is described for the direct synthesis of diaryl ketones via the C[sbnd]H bond activation of aldehydes using NiCu nanoparticles adorned on carbon nano onions as an efficient heterogeneous catalyst under the irradiation of a mercury-vapor lamp (400 w) via simple workup. This C[sbnd]H bond activation reaction appears simple and convenient with a wide substrate scope in view of its excellent synthesis prowess as illustrated in the preparation of new-approved anti-Alzheimer and anti-HIV medicinal compounds under greener and mild reaction conditions; catalyst could be recycled and reused five times without any loss of catalytic activity.
Heydari, Akbar,Khorsandi, Zahra,Metkazini, S. Fatemeh Mohammadi,Varma, Rajender S.
(2021/11/09)

Chiral electron-rich PNP ligand with a phospholane motif: Structural features and application in asymmetric hydrogenation
Despite the remarkable reactivity that was achieved by a series of transition-metal catalysts with a PNP type ligand, the electron-rich chiral PNP ligands have still been rarely reported because of the difficulties in synthesis and the nature of air-sensitivity. Herein, we report a novel chiral PNP ligand (Heng-PNP) with both a rigid backbone and a bulky tert-butyl group on the phospholane motif. We successfully obtained its divalent iron complex. The chiral environment of its Ir(III) complex was also discussed with quadrant analysis. This tridentate ligand was applied in iridium-catalyzed asymmetric hydrogenation of challenging diaryl ketones: up to 98% ee and 500 TON are achieved. Computational study showed that the twist of conjugate aryl group in the substrate (induced by the special chiral pocket of Ir/Heng-PNP complex) leads to the energy difference in the enantiodetermining step.
Wang, Heng,Zhang, Yao,Yang, Tilong,Guo, Xiaochong,Gong, Quan,Wen, Jialin,Zhang, Xumu
p. 8796 - 8801
(2020/11/13)

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)

Silylcarboxylic Acids as Bifunctional Reagents: Application in Palladium-Catalyzed External-CO-Free Carbonylative Cross-Coupling Reactions
A palladium-catalyzed external-CO-free carbonylative Hiyama-Denmark cross-coupling reaction is presented. The introduction of silylcarboxylic acids as bifunctional reagents (CO and nucleophile source) avoids the need for external gaseous CO and a silylarene coupling partner. The transformation features high functional group tolerance and it is successful with electron-rich, -neutral, and -poor aryl iodides. Stoichiometric studies and control experiments provide insight into the reaction mechanism and support the hypothesized dual role of silylcarboxylic acids. (Figure presented.).
Li, Xiong,Xu, Jie,Li, Yue,Kramer, S?ren,Skrydstrup, Troels,Lian, Zhong
p. 4078 - 4083
(2020/07/30)

N-Acylcarbazoles and N-Acylindoles: Electronically Activated Amides for N-C(O) Cross-Coupling by Nlpto Ar Conjugation Switch
The development of new amide precursors for selective, catalytic activation of carbon-nitrogen bonds in amides is a fundamental objective of this emerging reactivity manifold. We report the palladium-catalyzed Suzuki-Miyaura cross-coupling of N-acylcarbazoles and N-acylindoles with arylboronic acids by a highly selective N-C(O) cleavage. The key amide bond ground-state destabilization stems from Nlp to Ar conjugation and enables us for the first time to achieve reactivity similar to that for N-acylsulfonamide and N-acylcarbamate activation in simple anilides.
Buchspies, Jonathan,Rahman, Md. Mahbubur,Szostak, Roman,Szostak, Michal
supporting information
p. 4703 - 4709
(2020/06/17)

Xantphos-ligated palladium dithiolates: An unprecedented and convenient catalyst for the carbonylative Suzuki–Miyaura cross-coupling reaction with high turnover number and turnover frequency
Xantphos- and dithiolate-ligated macrocyclic palladium complexes as an efficient and stable catalyst for the carbonylative Suzuki–Miyaura cross-coupling reaction have been synthesized. The catalysts were characterized by 1H-nuclear magnetic resonance (NMR), CHNS (carbon, hydrogen, nitrogen, and sulfur) analysis, melting point analysis, and 31P-NMR spectroscopy. Several sensitive functional groups (e.g., –NO2, –F, –Cl, –Br, –NH2, and –CN) on the aromatic ring were well tolerated in the carbonylative Suzuki–Miyaura coupling reaction. The present palladium complexes produce six times higher turnover number (TON) and five times higher turnover frequency (TOF) compared with conventional homogeneous palladium precursors. Maximum TONs in the range of 105 to 106 and TOF in the range of 104 to 105 could be generated by a very low amount of catalyst loading (10–5?mol%).
Gaikwad, Vinayak V.,Mane, Pravin A.,Dey, Sandip,Bhanage, Bhalchandra M.
(2019/11/19)

Synthesis, structure, and characterization of picolyl- and benzyl-linked biphenyl palladium N-heterocyclic carbene complexes and their catalytic activity in acylative cross-coupling reactions
N-heterocyclic carbene ligands with picolyl (L1H2Br2, L3H2Br2) and benzyl (L2H2Br2, L4H2Br2) linked biphenyl backbone were synthesized and characterized. Their palladium(II) complexes [PdL1]Br2 (1), [PdL2Br2] (2), [PdL3]Br2 (3), and [PdL4Br2] (4) were synthesized by direct method using Pd(OAc)2. All complexes (1–4) were characterized by CHN analysis, electrospray ionization-MS, nuclear magnetic resonance, and single-crystal X-ray diffraction. Molecular structures confirm the distorted square planar geometry around the Pd(II) center. All of them showed good catalytic activity in acylative Suzuki cross coupling of phenyl boronic acid with benzoyl chloride to afford benzophenone in good yields.
Muniyappan, Nalluchamy,Sabiah, Shahulhameed
(2020/01/28)

The linkage between reversible Friedel–Crafts acyl rearrangements and the Scholl reaction
Friedel–Crafts acyl rearrangements in PPA (at 80–240?°C) and Scholl reactions in AlCl3/NaCl (at 140–220?°C) of benzoylnaphthalenes and fluorobenzoylnaphthalenes have been studied experimentally as a function of temperature and time and computationally. 1BzNA, 2BzNA, 1-4FBzNA, 2-4FBzNA, 1-3FBzNA, 2-3FBzNA, 1-2FBzNA, and 2-2FBzNA were synthesized by classical Friedel–Crafts acylations of naphthalene with benzoyl chloride, benzene with 2-naphthoyl chloride,?fluorobenzene with 1- and 2-naphthoyl chlorides and of naphthalene with fluorobenzoyl chlorides, and served as substrates in the investigation. Their structures have been determined by X-ray crystallography and verified by their 1H-, 13C-, and 19F-NMR spectra. 1BzNA, 1-4FBzNA, 1-3FBzNA, and 2-2FBzNA crystallized as the E-diastereomers, whereas 2BzAN, 1-2FBzAN, 2-4FBzAN, and 2-3FBzAN crystallized as the Z-diastereomers. The deviations of the carbonyl group from the naphthyl plane were higher as compared with the deviations from the phenyl plane and were considerably higher in the α-naphthyl ketones than in the β-naphthyl ketones. Intermolecular interactions due to C–H···O and/or C–H···F contacts in the crystal structures of 1E-4FBzNA and 1E1′E-3FBzAN have been revealed. 1BzNA rearranged in PPA under argon to 2BzNA via deacylation to naphthalene (e.g., 140?°C, 10?h) and underwent a regioselective intramolecular cyclodehydrogenation at high temperatures to the Scholl reaction product 7H-benz[de]anthracen-7-one (BdeAN) (e.g., 200?°C, 6?h). At 80?°C, benzene was isolated. 2BzNA underwent in PPA deacylation to naphthalene (e.g., 160?°C, 6?h) and an intramolecular cyclodehydrogenation to BdeAN at high temperatures (e.g., 220?°C, 6?h), necessarily via the putative intermediate 1BzNA. Higher yields of the acyl rearrangement and the Scholl reaction products were obtained under oxygen. 1-4FBzNA and 2-4FBzNA reacted in PPA analogously to 1BzNA and 2BzNA, respectively, with the following exceptions: 2-4FBzNA underwent an acyl rearrangement in PPA to 1-4FBzNA at 260–300?°C, without any formation of the Scholl reaction product 10FBdeAN. 1-4FBzNA also did not yield 10FBdeAN. 1-2FBzNA and 2-2FBzNA behaved similarly. The formation of naphthalene and benzene in the deacylation steps indicated cleavages of both the 1- and 2-naphthyl–benzoyl bonds and the 1- and 2-naphthoyl–phenyl bonds to give naphthalene and benzoylium cation and benzene and 1- and 2-naphthoylium cation, respectively. At 80–100?°C, 1-2FBzNA, 1-3FBzNA, and 1-4FBzNA underwent deacylations to fluorobenzene in PPA, followed by reacylation, each giving a mixture of the three 1-fluorobenzoylnaphthalenes. 2FBzNA, 2-3FBzNA, and 2-4FBzNA behaved similarly, each giving a mixture of the three 2-fluorobenzoylnaphthalenes. The results taken together verified the reversibility of the 1-BzNA?2BzNA acyl rearrangements in PPA. The Scholl reaction (AlCl3/NaCl) of 1BzNA (e.g., at 140?°C) gave BdeAN and 2BzNA, whereas 2BzNA gave only BdeAN (at 200–220?°C). 1-4FBzNA and 2-4FBzNA gave (at 200–220?°C) only 2-4FBzNA and 1-4FBzNA, respectively. All the six FBzNA isomers failed to undergo Scholl reaction cyclodehydrogenations to give any FBdeAN isomer. A linkage between the Friedel–Crafts acyl rearrangements and the Scholl reaction has thus been established. A systematic DFT study at B3LYP/6-311(d,p)/PCM (formic acid)) substantiated the predicted mechanism and the reversibility of the acyl rearrangements of benzoylnaphthalenes, in which 1BzNA and 2BzNA are the kinetically controlled and the thermodynamically controlled products, respectively. The DFT-calculated Gibbs free-energy of the transition-state (1Z-1BzNH+ ?? 2σ-2BzNA) in the Friedel–Crafts acyl rearrangement of 1Z-BzNA is considerably lower than the transition state of the cyclization step in the arenium-cation mechanism of the Scholl reaction, in line with experiment, which indicated higher temperatures for the Scholl reaction. DFT calculations of the dication pathway of the Scholl reaction of the E- and Z-diastereomers/conformers of 1BzNA confirmed the preference of the formation of BdeAN versus BaFL, consistently with experiment.
Agranat, Israel,Oded, Yaacov Netanel,Mala’bi, Tahani,Pogodin, Sergey,Cohen, Shmuel
p. 1579 - 1610
(2019/07/29)

Chemoselective Synthesis of Aryl Ketones from Amides and Grignard Reagents via C(O)-N Bond Cleavage under Catalyst-Free Conditions
Conversion of a wide range of N-Boc amides to aryl ketones was achieved with Grignard reagents via chemoselective C(O)-N bond cleavage. The reactions proceeded under catalyst-free conditions with different aryl, alkyl, and alkynyl Grignard reagents. α-Ketoamide was successfully converted to aryl diketones, while α,β-unsaturated amide underwent 1,4-addition followed by C(O)-N bond cleavage to provide diaryl propiophenones. N-Boc amides displayed higher reactivity than Weinreb amides with Grignard reagents. A broad substrate scope, excellent yields, and quick conversion are important features of this methodology.
Sureshbabu, Popuri,Azeez, Sadaf,Muniyappan, Nalluchamy,Sabiah, Shahulhameed,Kandasamy, Jeyakumar
p. 11823 - 11838
(2019/10/02)

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)

Ketone Synthesis by a Nickel-Catalyzed Dehydrogenative Cross-Coupling of Primary Alcohols
An intermolecular coupling of primary alcohols and organotriflates has been developed to provide ketones by the action of a Ni(0) catalyst. This oxidative transformation is proposed to occur by the union of three distinct catalytic cycles. Two competitive oxidation processes generate aldehyde in situ via hydrogen transfer oxidation or (pseudo)dehalogenation pathways. As aldehyde forms, a Ni-catalyzed carbonyl-Heck process enables formation of the key carbon-carbon bond. The utility of this rare alcohol to ketone transformation is demonstrated through the synthesis of diverse complex and bioactive molecules.
Verheyen, Thomas,Van Turnhout, Lars,Vandavasi, Jaya Kishore,Isbrandt, Eric S.,De Borggraeve, Wim M.,Newman, Stephen G.
supporting information

(2019/05/08)

Ketone Synthesis by a Nickel-Catalyzed Dehydrogenative Cross-Coupling of Primary Alcohols
An intermolecular coupling of primary alcohols and organotriflates has been developed to provide ketones by the action of a Ni(0) catalyst. This oxidative transformation is proposed to occur by the union of three distinct catalytic cycles. Two competitive oxidation processes generate aldehyde in situ via hydrogen transfer oxidation or (pseudo)dehalogenation pathways. As aldehyde forms, a Ni-catalyzed carbonyl-Heck process enables formation of the key carbon-carbon bond. The utility of this rare alcohol to ketone transformation is demonstrated through the synthesis of diverse complex and bioactive molecules.
Verheyen, Thomas,Van Turnhout, Lars,Vandavasi, Jaya Kishore,Isbrandt, Eric S.,De Borggraeve, Wim M.,Newman, Stephen G.
supporting information
p. 6869 - 6874
(2019/05/10)

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)

Transition-metal-free carbonylation of aryl halides with arylboronic acids by utilizing stoichiometric CHCl3 as the carbon monoxide-precursor
Under transition-metal-free conditions, carbonylative Suzuki couplings of aryl halides with arylboronic acid using stoichiometric CHCl3 as the carbonyl source has been developed. The simple, efficient, and environmentally benign method was successfully applied to the synthesis of Fenofibric acid, naphthyl phenstatin, and carbon-13 labeled biaryl ketone.
Xu, Fangning,Li, Dan,Han, Wei
supporting information
p. 2911 - 2915
(2019/06/18)

A convenient and practical heterogeneous palladium-catalyzed carbonylative Suzuki coupling of aryl iodides with formic acid as carbon monoxide source
A practical heterogeneous palladium-catalyzed carbonylative Suzuki coupling of aryl iodides with arylboronic acids under carbon monoxide gas-free conditions has been developed using a bidentate phosphino-functionalized magnetic nanoparticle-immobilized palladium(II) complex as catalyst. Formic acid was utilized as the carbon monoxide source with dicyclohexylcarbodiimide as the activator, and a wide variety of biaryl ketones were generated in moderate to high yields. The new heterogeneous palladium catalyst can be prepared via a simple procedure and can easily be separated from a reaction mixture by simply applying an external magnet and recycled up to 10 times without any loss of activity.
You, Shengyong,Yan, Chenyu,Zhang, Rongli,Cai, Mingzhong
(2019/01/04)

Method for catalytically dehydrogenating and oxidizing aryl secondary alcohol into ketone
The invention discloses a method for catalytically dehydrogenating and oxidizing aryl secondary alcohol into ketone. The method comprises the following steps: dissolving the aryl secondary alcohol inan organic solvent, and reacting at 40-120 DEG C in the presence of an acid catalyst and a cocatalyst to obtain substituted aryl ketone, wherein the acid is aryl sulfonic acid (ArSO3H), alkyl sulfonicacid (RSO3H) or boron trifluoride diethyl ether, and the cocatalyst is tertiary halogenated hydrocarbon or benzyl halogenated hydrocarbon. According to the method, a metal catalyst and an oxidizing agent are not used, the adopted catalyst is cheap and non-toxic and can tolerate water and air, the reaction condition is mild, and the method is simple to operate and high in atom economy, and can beused for large scale production.
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Paragraph 0028; 0037-0040

(2019/12/02)

N-heterocyclic carbene palladium(II)-catalyzed Suzuki-Miyaura cross coupling of N-acylsuccinimides by C-N cleavage
An easily prepared, well-defined N-heterocyclic carbene-palladium(II) complex was found to be an efficient catalyst for the Suzuki-Miyaura cross-coupling of N-acylsuccinimides with arylboronic acids via C-N bond activation. Under the optimal conditions, a
Guo, Han,Guo, Jiarui,Jia, Dingli,Liu, Lantao,Wang, Hengjin,Wang, Tao,Zhang, Wen
p. 80 - 84
(2018/10/20)

Extending the scope of the carbonyl facilitated triplet excited state towards visible light excitation
A series of extended π-conjugated benzophenone analogs was synthesized through a facile Lewis-acid catalyzed Friedel-Crafts reaction in order to exploit the integral triplet state properties of benzophenone. Extending the π-conjugated plane of the phenyl ring of benzophenone allowed tuning of the excitation wavelength from the far-UV end (～260 nm) to the visible spectrum (～446 nm). Compared to benzophenone, significant red-shifts in the absorption (up to 450 nm in solution) with high photostability were observed for the synthesized benzophenone analogs. As is evident from the density functional theory calculations, expansion of the ring size of the aromatic part of the benzophenone analogs induces a decrease in the HOMO-LUMO gap. The considerable extension of the electron density to the carbonyl group in the LUMO substantiates the triplet nature associated with the benzophenone analogs. By virtue of the properties of the carbonyl functionality, an apparent increase in the triplet quantum yield (ΦT = 5.4% to 87.7%) was observed for the benzophenone analogs when compared to the corresponding bare polyaromatic hydrocarbon. The spin orbit coupling was computationally estimated for the benzophenone analogs to propose pathways for the observed intersystem crossing process. The plausibility to photoexcite the aromatic-ring-fused benzophenone frameworks for triplet activation in the visible range opens the door for a new class of materials for photonic application.
Rajagopal, Shinaj K.,Nagaraj,Deb, Somadrita,Bhat, Vinayak,Sasikumar, Devika,Sebastian, Ebin,Hariharan, Mahesh
p. 19120 - 19128
(2018/08/07)

Hydrogen bond directed aerobic oxidation of amines via photoredox catalysis
An application of H-bonding interactions for directing the α-C-H oxidation of amines to amides and amino-ketones catalyzed by an organic photocatalyst is reported. The high efficiency of this method is demonstrated by the aerobic oxidation of pyrrolidines, diarylamines and benzylamines bearing urea groups with high yields and a wide substrate scope.
Wang, Hongyu,Man, Yunquan,Wang, Kaiye,Wan, Xiuyan,Tong, Lili,Li, Na,Tang, Bo
supporting information
p. 10989 - 10992
(2018/10/08)

Acyl and Decarbonylative Suzuki Coupling of N-Acetyl Amides: Electronic Tuning of Twisted, Acyclic Amides in Catalytic Carbon-Nitrogen Bond Cleavage
We report the Pd-catalyzed acyl and the Ni-catalyzed biaryl Suzuki-Miyaura cross-coupling of N-acetyl-amides with arylboronic acids by selective N-C(O) cleavage. Activation of the amide bond by N-acylation provides electronically destabilized, acyclic, nonplanar amide, which readily undergoes cross-coupling with a wide range of boronic acids to produce biaryl ketones or biaryls in a highly efficient manner. Most crucially, the presented results introduce N-acetyl-amides as reactive acyclic amides in the emerging manifold of transition-metal-catalyzed amide cross-coupling. The scope and origin of high selectivity are discussed. Mechanistic studies point to remodeling of amidic resonance and amide bond twist as selectivity determining features in a unified strategy for cross-coupling of acyclic amides. Structural studies, mechanistic investigations as well as beneficial effects of the N-acyl substitution on cross-coupling of amides are reported.
Liu, Chengwei,Li, Guangchen,Shi, Shicheng,Meng, Guangrong,Lalancette, Roger,Szostak, Roman,Szostak, Michal
p. 9131 - 9139
(2018/09/21)

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)

Pd(II)-Catalyzed Denitrogenative and Desulfinative Addition of Arylsulfonyl Hydrazides with Nitriles
A Pd(II)-catalyzed denitrogenative and desulfinative addition of arylsulfonyl hydrazides with nitriles has been successfully achieved under mild conditions. This transformation is a new method for the addition reaction to nitriles with arylsulfonyl hydrazides as arylating agent, thus providing an alternative synthesis of aryl ketones. The reported addition reaction is tolerant to many common functional groups, and works well in the presence of electron-donating and electron-withdrawing substituents. Notably, the reported denitrogenative and desulfinative addition was also appropriate for alkyl nitriles, making this newly developed transformation attractive.
Meng, Mengting,Yang, Liangfeng,Cheng, Kai,Qi, Chenze
p. 3275 - 3284
(2018/03/25)

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)

Pd-NHC catalysed Carbonylative Suzuki coupling reaction and its application towards the synthesis of biologically active 3-aroylquinolin-4 (1H)-one and acridone scaffolds
We have unfolded a convenient and mild protocol for the synthesis of diaryl ketones via Pd- NHC catalysed carbonylative Suzuki coupling reaction. Notably, this method offers advantages like no use of toxic CO gas, shorter reaction time, high yield, and broad substrate scope. Several sensitive functional groups (like-COMe, -COOMe, -F, -Cl, -Br, -NH2, -CN) are well tolerated in this reaction. In addition, we have also demonstrated a new efficient route for the synthesis of biologically active and pharmaceutically important 2-substituted 3-Aroylquinolin-4(1H)-ones and acridone scaffolds.
Ghosh, Prasanjit,Ganguly, Bhaskar,Das, Sajal
(2018/03/01)

Rapidly Activating Pd-Precatalyst for Suzuki-Miyaura and Buchwald-Hartwig Couplings of Aryl Esters
Esters are valuable electrophiles for cross-coupling due to their ubiquity and ease of synthesis. However, harsh conditions are traditionally required for the effective cross-coupling of ester substrates. Utilizing a recently discovered precatalyst, Pd-catalyzed Suzuki-Miyaura and Buchwald-Hartwig reactions involving cleavage of the C(acyl)-O bond of aryl esters that proceed under mild conditions are reported. The Pd(II) precatalyst is highly active because it is reduced to the Pd(0) active species more rapidly than previous precatalysts.
Dardir, Amira H.,Melvin, Patrick R.,Davis, Ryan. M.,Hazari, Nilay,Mohadjer Beromi, Megan
supporting information
p. 469 - 477
(2018/02/19)

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)

Palladium-catalyzed synthesis of diaryl ketones from aldehydes and (hetero)aryl halides via C-H bond activation
We developed a palladium-catalyzed C-H transformation that enabled the synthesis of ketones from aldehydes and (hetero)aryl halides. The use of picolinamide ligands was key to achieving the transformation. Heteroaryl ketones, as well as diaryl ketones, were synthesized in good to excellent yields, even in gram-scale, using this reaction. Results of density functional theory (DFT) calculations support the C-H bond activation pathway.
Wakaki, Takayuki,Togo, Takaya,Yoshidome, Daisuke,Kuninobu, Yoichiro,Kanai, Motomu
p. 3123 - 3128
(2018/04/14)

Preparation method of aromatic ketone
The invention discloses a preparation method of aromatic ketone. Under the effects of a palladium catalyst and a nitrogen-containing ligand, nitrile compounds and arylsulfonylhydrazide take desulfurization addition reaction in an organic solvent; after the reaction is completed, post treatment is performed to obtain aromatic ketone. The reaction is applicable to aromatic nitrile compounds, and isalso applicable to aliphatic nitrile compounds; the reaction realizes the wide substrate applicability and functional group tolerance; the potential application value is realized in the aspect of aryl-carbonyl building.
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Paragraph 0046; 0047; 0048; 0050

(2018/09/11)

Organoselenium-Catalyzed Oxidative C=C Bond Cleavage: A Relatively Green Oxidation of Alkenes into Carbonyl Compounds with Hydrogen Peroxide
A relatively green oxidative C=C bond cleavage of alkenes was achieved by organoselenium-catalyzed alkene oxidation reaction in ethanol with hydrogen peroxide, affording carbonyl compounds under relatively mild conditions. It is a new reaction style for the organoselenium-catalyzed oxidation of alkenes and largely contributes to the growing field of organoselenium catalysis.
Wang, Tingting,Jing, Xiaobi,Chen, Chao,Yu, Lei
p. 9342 - 9349
(2017/09/23)

N-Acylsuccinimides: Efficient acylative coupling reagents in palladium-catalyzed Suzuki coupling via C–N cleavage
An acylative Suzuki coupling of activated amides with aryl boronic acids has been reported via palladium-catalyzed C–N bond cleavage. This protocol demonstrate amides can be activated by an atom-economic and cheap succinimide, which can be efficiently utilized to synthesize broad array of diaryl ketones in moderate to good yields.
Cui, Ming,Chen, Zeyu,Liu, Tingting,Wang, Hui,Zeng, Zhuo
supporting information
p. 3819 - 3822
(2017/09/15)

Acid fluorides as acyl electrophiles in suzuki–miyaura coupling
The first palladium-catalyzed construction of ketones through Suzuki–Miyaura reaction by using acid fluorides is described. In contrast to typical acyl electrophiles such as acid chlorides, acid fluorides are uncommon acyl electrophiles to use in boron-based coupling reactions, probably due to a high level of stability toward nucleophiles. This first attempt to use acid fluorides as a coupling partner with boronic acids allowed highly functional group tolerance and a wide substrate scope while affording various ketones in effective yields.
Ogiwara, Yohei,Sakino, Daisuke,Sakurai, Yuka,Sakai, Norio
supporting information
p. 4324 - 4327
(2018/08/28)

General Method for the Suzuki-Miyaura Cross-Coupling of Primary Amide-Derived Electrophiles Enabled by [Pd(NHC)(cin)Cl] at Room Temperature
A general, highly selective method for the room temperature Suzuki-Miyaura cross-coupling of commonly encountered primary benzamides is reported. A combination of site-selective N,N-di-Boc-activation (tert-butoxycarbonyl activation) of the amide nitrogen with practical air- and moisture-stable, well-defined, and highly reactive [Pd(NHC)(cin)Cl] (NHC = N-heterocyclic carbene; cin = cinnamyl) provides a highly effective route to biaryl ketones from primary amides in high yields. For the first time, a TON of >1000 has been achieved in amide acyl cross-coupling.
Lei, Peng,Meng, Guangrong,Ling, Yun,An, Jie,Nolan, Steven P.,Szostak, Michal
supporting information
p. 6510 - 6513
(2017/12/26)

A phosphine-free, heterogeneous palladium-catalyzed atom-efficient carbonylative cross-coupling of triorganoindiums with aryl halides leading to unsymmetrical ketones
The first phosphine-free heterogeneous palladium-catalyzed carbonylative cross-coupling of aryl halides with triorganoindiums has been developed that proceeds smoothly under 1 or 2.5 atm of carbon monoxide in THF at 68 °C and provides a general and powerful tool for the synthesis of various valuable unsymmetrical ketones with high atom-economy, good yield, and recyclability of the catalyst. Our system not only avoids the use of phosphine ligands, but also solves the basic problem of palladium catalyst recovery and reuse.
You, Shengyong,Xiao, Ruian,Liu, Haiyi,Cai, Mingzhong
p. 13862 - 13870
(2017/11/27)

N-Methylamino Pyrimidyl Amides (MAPA): Highly Reactive, Electronically-Activated Amides in Catalytic N-C(O) Cleavage
Despite recent progress in catalytic cross-coupling technologies, the direct activation of N-alkyl-N-aryl amides has been a challenging transformation. Here, we report the first Suzuki cross-coupling of N-methylamino pyrimidyl amides (MAPA) enabled by the controlled nN → πAr conjugation and the resulting remodeling of the partial double bond character of the amide bond. The new mode of amide activation is suitable for generating acyl-metal intermediates from unactivated primary and secondary amides.
Meng, Guangrong,Lalancette, Roger,Szostak, Roman,Szostak, Michal
p. 4656 - 4659
(2017/09/12)

A phosphine-free, atom-efficient cross-coupling reaction of triorganoindiums with acyl chlorides catalyzed by immobilization of palladium(0) in MCM-41
The first phosphine-free heterogeneous palladium(0)-catalyzed cross-coupling of triorganoindiums with acyl chlorides has been developed that proceeds smoothly in THF at 68 °C and provides a general and powerful tool for the synthesis of various valuable aryl ketones and α,β-acetylenic ketones with high atom-economy and high yield. This phosphine-free heterogeneous palladium(0) catalyst can be easily prepared from commercially available reagents and recovered by a simple filtration of the reaction solution and used for at least 10 consecutive trials without any decreases in activity. Our system not only avoids the use of phosphine ligands, but also solves the basic problem of palladium catalyst recovery and reuse.
Miao, Jiankang,Huang, Bin,Liu, Haiyi,Cai, Mingzhong
p. 42570 - 42578
(2017/09/11)

A synthesis of biaryl ketones via the C–S bond cleavage of thiol ester by a Cu/Ag salt
We report the synthesis of biaryl ketones via an unprecedented copper/silver catalyzed acylative cross-coupling of thiol esters with either an arylboronic acid or a potassium aryltrifluoroborate. This new method proceeds without a requisite Pd-catalyst and Cu(I)TC mediator, and is efficient, versatile, operationally simple, and accommodating functionally diverse thiol esters, arylboronic acids, and potassium aryltrifluoroborates.
Ghosh, Prasanjit,Ganguly, Bhaskar,Das, Sajal,Perl, Eliyahu
p. 2751 - 2756
(2017/06/23)

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)

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
supporting information
p. 2536 - 2539
(2017/05/24)

Palladium-Catalyzed Suzuki-Miyaura Cross-Coupling of N-Mesylamides by N-C Cleavage: Electronic Effect of the Mesyl Group
A general Pd-catalyzed Suzuki-Miyaura cross-coupling of N-mesylamides with arylboronic acids by selective N-C cleavage has been developed. The presented results represent the first example of a transition-metal-catalyzed cross-coupling of amides activated by an atom-economic, cheap, and benign mesyl group. The reaction delivers arylated products featuring a range of useful functional groups by chemoselective cleavage of the amide N-C bond with high efficiency. Both the scope and the origin of high selectivity are discussed. A beneficial effect of the N-mesyl substituent on the bond activation in acyclic amides is presented.
Liu, Chengwei,Liu, Yongmei,Liu, Ruzhang,Lalancette, Roger,Szostak, Roman,Szostak, Michal
supporting information
p. 1434 - 1437
(2017/03/23)

Synthesis and structural characterization of Pd(II) thiosemicarbazonato complex: Catalytic evaluation in synthesis of diaryl ketones from aryl aldehydes and arylboronic acids
A simple route to synthesize triphenylphosphinopalladium(II) thiosemicarbazonato complex has been described. Elemental analysis, spectral (IR, NMR) and single crystal X-ray diffraction techniques were employed for the complete characterization of the complex. The latter was found to be effective catalyst for carbon–carbon cross-coupling reaction of aryl- and heteroarylboronic acids with aromatic and heteroaromatic aldehydes to form the corresponding diaryl ketones. The influence of reaction parameters such as solvent, base, reaction temperature and catalyst loading was also investigated.
Prabhu, Rupesh Narayana,Ramesh, Rengan
supporting information
p. 405 - 409
(2017/01/10)

Carbonylative Suzuki Coupling Reaction Catalyzed by a Hydrospirophosphorane Palladium Complex
A Pd complex with the H-spirophosphorane ligand, PdCl2{P(OCMe2CMe2O)OC6H4NH2} (Cat. 1), was used as the catalyst in the carbonylative Suzuki coupling of substituted iodobenzenes with arylboronic acids and with sodium tetraphenylborate. Substituted diarylketones were obtained in good to excellent yields and a selectivity over 95 % under 1 atm of CO with 1.5 mol % of the catalyst. The promoting role of the H-spirophosphorane ligand in the catalytic process was evidenced. We used X-ray photoelectron spectroscopy, TEM, and 31P NMR spectroscopy to reveal that during the reaction Cat. 1 undergoes transformation into Pd complexes that bear the spirophosphorane ligand or other P ligands formed by its dealkylation and to Pd nanoparticles. All these Pd species contribute to the high productivity of the system.
Wójcik, Przemys?aw,Sygellou, Labrini,Gniewek, Andrzej,Skar?yńska, Anna,Trzeciak, Anna
p. 4397 - 4409
(2017/11/21)

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)

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 0026; 0027; 0030

(2017/07/14)

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; 0020-0026

(2017/08/02)

A gassing by olefin method
The invention provides a simple synthetic method for synthesizing a ketone from an olefin, and relates to the field of the synthetic technology of carbonyl compounds. The method includes the step that ceric ammonium nitrate serves as a catalyst, oxygen serves as an oxidizing agent, and the disubstituted terminal olefin is subjected to catalytic oxidation to prepare the carbonyl compound. Compared with a traditional method, the method is environmentally friendly and high in yield, reaction conditions are moderate, no ligand is used, the usage amount of the catalyst is small, a substrate is wide in application range, and the method is the simple synthetic method for synthesizing ketones.
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Paragraph 0016; 0037-0041

(2017/07/06)