cas 644-13-3, 2-NAPHTHYL PHENYL KETONE | Articles data

Articles about 644-13-3Total 142 be found

Article title
Article abstract
Author
Journal number and time
Download

Synthesis of aromatic ketones by a transition metal-catalyzed tandem sequence
Both simple Ag(I) and Au(I) are effective catalysts for a tandem [3,3]-sigmatropic rearrangement/formal Myers-Saito cyclization of propargyl esters to form aromatic ketones. A mechanism in which the metal catalyzes both of these processes through alkyne activation is proposed. By using this method a wide range of aromatic structures including naphthyl, anthracenyl and indole ketones are available from readily available propargyl esters. Copyright
Zhao, Jing,Hughes, Colin O.,Toste, F. Dean
p. 7436 - 7437
(2006)
Read Online

Synthesis of 2-acyl-3-arylnaphthalenes by dual catalysis of sodium tetrachloroaurate toward alkyne-propargylic acetates
A new and highly convenient Au-catalyzed cyclization of alkyne-propargylic acetates leading to 2-acyl-3-arylnaphthalene derivatives is described; these are possible candidates for light-emitting materials. Georg Thieme Verlag Stuttgart.
Oh, Chang Ho,Kim, Ahyun,Park, Wooram,Park, Dai In,Kim, Nakjoong
p. 2781 - 2784
(2006)
Read Online

Iterative addition of carbon nucleophiles toN,N-dialkyl carboxamides for synthesis of α-tertiary amines
A protocol for the synthesis of α-tertiary amines was developed by iterative addition of carbon nucleophiles toN,N-dialkyl carboxamides. Nucleophilic 1,2-addition of organolithium reagents to carboxamides forms anionic tetrahedral carbinolamine (hemiaminal) intermediates, which are subsequently treated with bromotrimethylsilane (Me3SiBr) followed by organomagnesium (Grignard) reagents, organolithium reagents or tetrabutylammonium cyanide, affording α-tertiary amines. Employment of (trimethylsilyl)methylmagnesium bromide as the 2ndnucleophile allowed for aza-Peterson olefination of the resulting α-tertiary (trimethylsilyl)methylamines with acidic work-up, resulting in the formation of 1,1-diarylethylenes.
Chen, Jiahua,Chiba, Shunsuke,Lim, Jun Wei,Ong, Derek Yiren
p. 99 - 104
(2022/01/06)

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)

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)

Acylboronates in polarity-reversed generation of acyl palladium(II) intermediates
We report a catalytic cross-coupling process between aryl (pseudo)halides and boron-based acyl anion equivalents. This mode of acylboronate reactivity represents polarity reversal, which is supported by the observation of tetracoordinated boronate and acyl palladium(II) species by 11B, 31P NMR, and mass spectrometry. A broad scope of aliphatic and aromatic acylboronates has been examined, as well as a variety of aryl (pseudo)halides.
Trofimova, Alina,Holownia, Aleksandra,Tien, Chieh-Hung,?irvinskas, Martynas J.,Yudin, Andrei K.
supporting information
p. 3294 - 3299
(2021/05/07)

Organotellurium-catalyzed oxidative deoximation reactions using visible-light as the precise driving energy
Irradiated by visible light, the recyclable (PhTe)2-catalyzed oxidative deoximation reaction could occur under mild conditions. In comparison with the thermo reaction, the method employed reduced catalyst loading (1 mol% vs. 2.5 mol%), but afforded elevated product yields with expanded substrate scope. This work demonstrated that for the organotellurium-catalyzed reactions, visible light might be an even more precise driving energy than heating because it could break the Te–Te bond accurately to generate the active free radical catalytic intermediates without damaging the fragile substituents (e.g., heterocycles) of substrates. The use of O2 instead of explosive H2O2 as oxidant affords safer reaction conditions from the large-scale application viewpoint.
Deng, Xin,Qian, Rongrong,Zhou, Hongwei,Yu, Lei
supporting information
p. 1029 - 1032
(2020/10/23)

AIBN initiated functionalization of the benzylic sp3 C[sbnd]H and C[sbnd]C bonds in the presence of dioxygen
A sp3 C[sbnd]H bond functionalization and C[sbnd]C bond cleavage were realized by AIBN/O2 catalyst system, providing a series of benzophenones under mild reaction conditions. The mechanistic study shows that a peroxide intermediate is involved in this transformation, and in the case of diphenylmethanes, the sp3 C[sbnd]C bond is cleaved through the peroxide rearrangement, which might provides a new way to cleave relatively strong C[sbnd]C bond and be applied to more general C[sbnd]C bond activation.
Hu, Yingying,Shao, Yu,Zhang, Shuwei,Yuan, Yuan,Sun, Zheng,Yuan, Yu,Jia, Xiaodong
supporting information

(2021/02/01)

Poly(ethylene glycol) dimethyl ether mediated oxidative scission of aromatic olefins to carbonyl compounds by molecular oxygen
A simple, and practical oxidative scission of aromatic olefins to carbonyl compounds using O2as the sole oxidant with poly(ethylene glycol) dimethyl ether as a benign solvent has been developed. A wide range of monosubstituted,gem-disubstituted, 1,2-disubstituted, trisubstituted and tetrasubstituted aromatic olefins was successfully converted into the corresponding aldehydes and ketones in excellent yields even with gram-scale reaction. Some control experiments were also conducted to support a possible reaction pathway.
Yu, Tao,Guo, Mingqing,Wen, Simiaomiao,Zhao, Rongrong,Wang, Jinlong,Sun, Yanli,Liu, Qixing,Zhou, Haifeng
p. 13848 - 13852
(2021/04/22)

Method for preparing aldehyde ketone compound through olefin oxidation
The invention provides a method for preparing an aldehyde ketone compound by olefin oxidation, which relates to an olefin oxidative cracking reaction in which oxygen participates. The method comprises the following specific steps: in the presence of a solvent and an oxidant, carrying out oxidative cracking on an olefin raw material to obtain a corresponding aldehyde ketone product. Compared with the traditional method, the method does not need to add any catalyst or ligand, does not need to use high-pressure oxygen, has the advantages of simple and mild reaction conditions, environment friendliness, low cost, high atom economy and the like, is wide in substrate application range and high in yield, and has a wide application prospect in the aspects of synthesis of aldehyde ketone medical intermediates and chemical raw materials.
-
Paragraph 0019

(2021/04/07)

Acyl radicals from α-keto acids using a carbonyl photocatalyst: Photoredox-catalyzed synthesis of ketones
Acyl radicals have been generated from α-keto acids using inexpensive and commercially available 2-chloro-thioxanthen-9-one as the photoredox catalyst under visible light illumination. These reactive species added to olefins or coupled with aryl halides via a bipyridylstabilized Ni(II) catalyst, enabling easy access to a diverse range of ketones. This reliable, atom-economical, and eco-friendly protocol is compatible with a wide range of functional groups.
Zhu, Da-Liang,Wu, Qi,Young, David James,Wang, Hao,Ren, Zhi-Gang,Li, Hong-Xi
supporting information
p. 6832 - 6837
(2020/10/12)

Palladium-Catalyzed Suzuki Coupling of N-Acyloxazolidinones via Selective Cleavage of C–N Bonds
By implementing a palladium-catalyzed Suzuki coupling reaction of N-acyloxazolidinones with arylboronic acid, we herein report on the preparation of substituted diaryl ketones via selective cleavage of exocyclic C–N Bonds. The reaction was carried out under mild reaction conditions with excellent functional group compatibility in good yields (up to 93 %).
Jian, Junsheng,He, Zhanyu,Zhang, Yuqi,Liu, Tingting,Liu, Lizhen,Wang, Zijia,Wang, Hui,Wang, Sanyong,Zeng, Zhuo
p. 4176 - 4180
(2020/07/13)

Scalable Aerobic Oxidation of Alcohols Using Catalytic DDQ/HNO3
A selective, practical, and scalable aerobic oxidation of alcohols is described that uses catalytic amounts of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and HNO3, with molecular oxygen serving as the terminal oxidant. The method was successfully applied to the oxidation of a wide range of benzylic, propargylic, and allylic alcohols, including two natural products, namely, carveol and podophyllotoxin. The conditions are also applicable to the selective oxidative deprotection of p-methoxybenzyl ethers.
Arseniyadis, Stellios,Clavier, Louis,Copin, Chloé,Fournier, Jean,Giffard, Jean-Fran?ois,Jean, Alexandre,Katsina, Tania,Macedo Portela Da Silva, Nayane,Tamion, Rodolphe
supporting information
p. 856 - 860
(2020/07/14)

Designing highly fluorescent, arylated poly(phenylene vinylene)s of intrinsic microporosity
Three new polymers containing tetraphenylethylene and diphenyl-dinaphthylethylene cores and their corresponding monomeric model compounds were synthesized and fully characterized aiming to investigate their photoluminescence efficiency, microporosity and Brunauer-Emmett-Teller-derived surface areas (SBET). Comprehensive photophysical characterization was undertaken in the solid state (powder and thin films), in tetrahydrofuran (THF) solution and in mixtures of "good" and "poor" solvent to induce aggregation (THF:water mixtures). Aggregation induced emission (AIE) was found for the tert-butyl-TPE monomer and polymer and diphenyl-dinaphthylethylene monomer with the increase of the water amount in THF:water mixtures and in the solid state. The tert-butyl substituted TPE derivatives display the highest fluorescence quantum yield (?F) values: 0.14 to 0.30 (in powder) and 0.46 to 0.64 in thin films. In contrast, with the diphenyl-dinaphthylethylene (meta and para-phenylene) polymers aggregation caused quenching (ACQ) occurs in THF:water mixtures (?F ≤ 0.011) and in the solid state (?F ≤ 0.012). The microporosity of the soluble conjugated polymers as potential conjugated polymers of intrinsic microporosity (cPIMs) was further investigated. The SBET of the polymers were related to their optical properties. The polymers show an attractive combination of high SBET surface area (417 m2 g-1) and the occurrence of distinct AIE effects for the tert-butyl-TPE polymer while the diphenyl-dinaphthylethylene polymers do not exhibit microporosity (SBET ≤ 17 m2 g-1) and show ACQ behavior.
Dreher, Elke,Geisler, Isabell S.,Klein, Patrick,Lehmann, Christian W.,Neuhaus, Fabian J. H.,Pina, Joa?,Rodrigues, Ana Clara B.,Sérgio Seixas De Melo, J.,Scherf, Ullrich
supporting information
p. 2248 - 2257
(2020/03/04)

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)

Copper-Catalyzed Oxidative Fragmentation of Alkynes with NFSI Provides Aryl Ketones
A copper-catalyzed oxidative cleavage reaction of alkynes using NFSI and TBHP was described. Various terminal and internal alkyne substrates were employed to render quick access to aryl ketone products in moderate to good yields. NFSI not only functioned as N-centered radical precursors but also engaged in the aryl group migration. Mechanistic studies also suggested the important role of water in the title reactions.
Chen, Hanfei,Cheng, Hao,Huang, Yifan,Jin, Chaochao,Song, Weihan,Tan, Chen,Tan, Jiajing,Tang, Lin,Yang, Fang,Zhang, Shuaifei
supporting information

(2020/11/03)

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)

Ionic liquid-mediated benzoyl transfer-coupling in the Suzuki and Sonogashira reactions and aryl transfer-coupling by decarbonylative Heck reaction, using N-Benzoyl-saccharin (NBSac) as reagent
The efficacy of N-benzoyl-saccharin (NBSac) as reagent for selective benzoyl transfer-coupling in the Suzuki reaction in BMIM-IL/[PAIM][NTf2] as solvent/base, and in the Sonogashira reaction employing guanidinium-IL (GIL) as solvent, are demonstrated. Decarbonylative aryl transfer-coupling occurs in the Heck reaction employing GIL as solvent. The reactions are catalyzed by Pd(OAc)2 or NiCl2(dppp), are performed under mild conditions in good yields, and have the potential for recycling/reuse of the IL solvent. Collectively, these methods provide facile access to diverse libraries of diarylketones, keto-ethynes and diaryl-ethenes.
Malunavar, Shruti S.,Sutar, Suraj M.,Prabhala, Pavankumar,Kalkhambkar, Rajesh G.,Laali, Kenneth K.
supporting information

(2020/05/18)

Synthesis of biaryl ketones by arylation of Weinreb amides with functionalized Grignard reagents under thermodynamic controlvs.kinetic control ofN,N-Boc2-amides
A highly efficient method for chemoselective synthesis of biaryl ketones by arylation of Weinreb amides (N-methoxy-N-methylamides) with functionalized Grignard reagents is reported. This protocol offers rapid entry to functionalized biaryl ketones after Mg/halide exchange with i-PrMgCl·LiCl under operationally-simple and practical reaction conditions. The scope of the method is highlighted in >40 examples, including bioactive compounds and pharmaceutical derivatives. Collectively, this transition-metal-free approach offers a major advantage over the recently established cross-coupling of amides by oxidative addition of N-C(O) bonds. Considering the utility of amide acylation reactions in modern synthesis, we expect that this method will be of broad interest.
Li, Guangchen,Szostak, Michal
supporting information
p. 3827 - 3831
(2020/06/03)

Water Phase, Room Temperature, Ligand-Free Suzuki–Miyaura Cross-Coupling: A Green Gateway to Aryl Ketones by C–N Bond Cleavage
We report herein a green strategy for synthesis of aryl ketones from twisted amides by using Pd(OAc)2 as catalysts. This method shows high functional group tolerance to offer a variety of ketones in good yields under mild conditions (up to 94 %). Notably, this methodology demonstrates the first water phase, room temperature, ligand-free Suzuki–Miyaura coupling through C–N bond cleavage, which is environmentally friendly and might facilitate the development of amide based green chemistry.
Zhang, Yuqi,Wang, Zijia,Tang, Zhao,Luo, Zhongfeng,Wu, Hongxiang,Liu, Tingting,Zhu, Yulin,Zeng, Zhuo
p. 1620 - 1628
(2020/03/04)

Kinetically Controlled, Highly Chemoselective Acylation of Functionalized Grignard Reagents with Amides by N?C Cleavage
The direct transition-metal-free acylation of amides with functionalized Grignard reagents by highly chemoselective N?C cleavage under kinetic control has been accomplished. The method offers rapid and convergent access to functionalized biaryl ketones through transient tetrahedral intermediates. The direct access to functionalized Grignard reagents by in situ halogen–magnesium exchange promoted by the versatile turbo-Grignard reagent (iPrMgCl?LiCl) permits excellent substrate scope with respect to both the amide and Grignard coupling partners. These reactions enable facile, operationally simple and chemoselective access to tetrahedral intermediates from amides under significantly milder conditions than chelation-controlled intermediates. This novel direct two-component coupling sets the stage for using amides as acylating reagents in an alternative paradigm to the metal-chelated approach, acyl metals and Weinreb amides.
Li, Guangchen,Szostak, Michal
supporting information
p. 611 - 615
(2020/01/02)

N-Acyl-5,5-Dimethylhydantoins: Mild Acyl-Transfer Reagents for the Synthesis of Ketones Using Pd-PEPPSI or Pd/Phosphine Catalysts
N-Acyl-hydantoins have emerged as novel acyl-transfer reagents for the synthesis of ketones via selective N-C(O) cleavage. Herein, we report two new protocols for the cross-coupling of N-acyl-5,5-dimethylhydantoins using versatile and readily accessible Pd-PEPPSI or Pd/phosphine catalysts. The acyl Suzuki reactions afford biaryl ketones in good to excellent yields under operationally simple conditions using commercially available, bench- A nd air-stable twisted N-acyl-hydantoins as acyl donors. The method complements and expands on the previous protocol for the cross-coupling of N-acyl-hydantoins (Luo, Z.et al. Org. Process Res. Dev. 2018, 22, 1188).
Liu, Chengwei,Szostak, Michal,Wang, Chang-An
p. 1043 - 1051
(2020/07/15)

Suzuki-Miyaura Cross-Coupling of Amides using Well-Defined, Air-Stable [(PR3)2Pd(II)X2] Precatalysts
A versatile method for the Suzuki-Miyaura cross-coupling of amides using highly active, well-defined, and air-stable Pd?phosphine precatalysts is reported. Most notably, the method represents the first example of using practical and operationally-simple Pd(II)?phosphine precatalysts in the emerging amide bond cross-coupling manifold. The reactions are efficient at 0.10 mol% loading, furnishing biaryl ketones with high chemoselectivity for N?C(O) bond cleavage. This versatile method enables for the first time to achieve Pd?phosphine-catalyzed cross-coupling of amides at ppm loading. This C?N cross-coupling can be used to efficiently furnish pharmaceutical intermediates by orthogonal Pd-catalyzed cross-couplings. We fully expect that operationally-simple [(PR3)2Pd(II)X2] precatalysts as effective triggers for N?C(O) cross-coupling will be of broad synthetic and catalytic interest. (Figure presented.).
Li, Guangchen,Ma, Siyue,Szostak, Michal,Zhou, Tongliang
supporting information

(2020/05/26)

A Bifunctional Iron Nanocomposite Catalyst for Efficient Oxidation of Alkenes to Ketones and 1,2-Diketones
We herein report the fabrication of a bifunctional iron nanocomposite catalyst, in which two catalytically active sites of Fe-Nx and Fe phosphate, as oxidation and Lewis acid sites, were simultaneously integrated into a hierarchical N,P-dual doped porous carbon. As a bifunctional catalyst, it exhibited high efficiency for direct oxidative cleavage of alkenes into ketones or their oxidation into 1,2-diketones with a broad substrate scope and high functional group tolerance using TBHP as the oxidant in water under mild reaction conditions. Furthermore, it could be easily recovered for successive recycling without appreciable loss of activity. Mechanistic studies disclose that the direct oxidation of alkenes proceeds via the formation of an epoxide as intermediate followed by either acid-catalyzed Meinwald rearrangement to give ketones with one carbon shorter or nucleophilic ring-opening to generate 1,2-diketones in a cascade manner. This study not only opens up a fancy pathway in the rational design of Fe-N-C catalysts but also offers a simple and efficient method for accessing industrially important ketones and 1,2-diketones from alkenes in a cost-effective and environmentally benign fashion.
Ma, Zhiming,Ren, Peng,Song, Tao,Xiao, Jianliang,Yang, Yong,Yuan, Youzhu
p. 4617 - 4629
(2020/05/19)

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)

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)

Combined Photoredox/Enzymatic C?H Benzylic Hydroxylations
Chemical transformations that install heteroatoms into C?H bonds are of significant interest because they streamline the construction of value-added small molecules. Direct C?H oxyfunctionalization, or the one step conversion of a C?H bond to a C?O bond, could be a highly enabling transformation due to the prevalence of the resulting enantioenriched alcohols in pharmaceuticals and natural products,. Here we report a single-flask photoredox/enzymatic process for direct C?H hydroxylation that proceeds with broad reactivity, chemoselectivity and enantioselectivity. This unified strategy advances general photoredox and enzymatic catalysis synergy and enables chemoenzymatic processes for powerful and selective oxidative transformations.
Betori, Rick C.,May, Catherine M.,Scheidt, Karl A.
supporting information
p. 16490 - 16494
(2019/11/03)

Beyond the Corey–Chaykovsky Reaction: Synthesis of Unusual Cyclopropanoids via Desymmetrization and Thereof
Desymmetrization-based protocols for the synthesis of highly functionalized indeno-spirocyclopropanes and cyclopropa-fused indanes have been established through unexpected reactions triggered by the Corey–Chaykovsky reagent. These structures were further elaborated in one step to privileged scaffolds such as fluorenones, indenones, and naphthaphenones. For instance, an acid-catalyzed transformation of indeno-spirocyclopropanes provided fluorenones via a homo-Nazarov-type cyclization, and naphthaphenones were obtained via an acid-catalyzed cyclopropane ring-opening/retro-Michael sequence.
Patel, Kaushalendra,Mishra, Uttam K.,Mukhopadhyay, Dipto,Ramasastry
supporting information
p. 4568 - 4571
(2019/11/03)

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)

COMPOUND FOR ORGANIC SYNTHETIC REACTION
PROBLEM TO BE SOLVED: To provide a compound for organic synthetic reaction capable of reducing unnecessary reaction byproduct and generating a targeted chemical reaction effectively, even when a base compound sensitive to basicity is used. SOLUTION: There is provided a compound for organic synthetic reaction which is used for a coupling reaction or an addition reaction forming a bond between carbon-carbon, and is a compound represented by the structure formula (1) or a salt thereof. In the formula, (A) represents an oxygen atom or a nitrogen atom, R1 represents a substituent containing one or more carbon atom, R2 represents a substituent containing one or more carbon atom, hydrogen or halogen, and R1 and R2 may be the same or different each other. SELECTED DRAWING: Figure 2 COPYRIGHT: (C)2019,JPOandINPIT
-
(2019/05/01)

Continuous flow synthesis of diaryl ketones by coupling of aryl Grignard reagents with acyl chlorides under mild conditions in the ecofriendly solvent 2-methyltetrahydrofuran
An efficient continuous flow sequential synthesis of diaryl ketones was achieved by coupling of aryl Grignard reagents with acyl chlorides in the bio-derived “green” solvent 2-methyltetrahydrofuran (2-MeTHF) under mild reaction conditions (ambient temperature, 1 hour), allowing a safe and on-demand generation of 2-(3-benzoylphenyl)propionitrile with a productivity of 3.16 g hour?1
Zhang, Chuan-Tao,Zhu, Rui,Wang, Zheng,Ma, Bing,Zajac, Adrian,Smiglak, Marcin,Xia, Chun-Nian,Castle, Steven L.,Wang, Wen-Long
p. 2199 - 2204
(2019/01/26)

N-Acyl-5,5-dimethylhydantoin, a New Mild Acyl-Transfer Reagent in Pd Catalysis: Highly Efficient Synthesis of Functionalized Ketones
The palladium-catalyzed Suzuki-Miyaura cross-coupling of N-acyl-5,5-dimethylhydantoins with arylboronic acids has been developed via selective amides C-N bond cleavage. The new reagent is commercially available and air-/moisture-stable, and it offers a variety of ketones in good yields through Suzuki coupling under mild conditions (up to 95%).
Luo, Zhongfeng,Liu, Tingting,Guo, Weijie,Wang, Zijia,Huang, Jingjun,Zhu, Yulin,Zeng, Zhuo
p. 1188 - 1199
(2018/09/06)

Palladium-Catalyzed Ligand-Free Decarboxylative Coupling of α- Oxocarboxylic Acid with Aryl Diazonium Tetrafluoroborate: An Access to Unsymmetrical Diaryl Ketones
Diaryl ketones are of much importance in organic synthesis as versatile intermediates and in industry for their useful properties. A mild and efficient palladium-catalyzed traditional ligand-free decarboxylative coupling of aryl α-keto carboxylic acid with aryl diazonium fluoroborate has been developed. A series of unsymmetrical diaryl ketones has been synthesized in moderate to good yields using this procedure. A radical pathway involving the acyl radical has been suggested.
Panja, Subir,Maity, Pintu,Ranu, Brindaban C.
p. 12609 - 12618
(2018/10/20)

Palladium-Catalyzed Carbonylative Coupling Reactions of N,N-Bis(methanesulfonyl)amides through C–N Bond Cleavage
Palladium-catalyzed carbonylative coupling reactions of various N,N-bis(methanesulfonyl)amides with arylboronic acids through C–N bond cleavage were carried out. The reactions proceeded under mild conditions in a short period of time without any additives to afford a wide range of unsymmetrical aryl ketones in excellent yields. This is the first example of a carbonylative coupling reaction using N,N-bis(methanesulfonyl)amide as a coupling substrate.
Lim, Minkyung,Kim, Hyeji,Ban, Jaeyoung,Son, Junghan,Lee, Jae Kyun,Min, Sun-Joon,Lee, Sang Uck,Rhee, Hakjune
p. 5717 - 5724
(2018/09/29)

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)

Method of utilizing continuous flow microreactor to synthesize benzophenone derivative
The invention belongs to the technical field of organic synthesis, and particularly relates to a method of utilizing a continuous flow microreactor to synthesize a benzophenone derivative. The methodincludes: using aryl Grignard reagent and acyl chloride as raw materials; at normal temperature, continuously synthesizing the benzophenone derivative in the microreactor; recycling a reaction solvent2-methyl tetrahydrofuran. Problems of environmental pollution and reaction operation safety caused by the fact that conventional Fridel-Crafts reaction is excessively dependent on reagents like aluminum trichloride, ferric trichloride and zinc dichloride are avoided, the defect that novel catalytic processes are expensive in catalytic reagent and harsh in operation condition is made up, and continuous synthesis of a medical intermediate ketoprofen nitrile is realized efficiently. The method has the advantages of high operation convenience, high reaction safety, high yield, high efficiency andreaction solvent reusability and is environment-friendly and efficient.
-
Paragraph 0041-0044; 0047

(2018/09/11)

Pd-Catalyzed Suzuki–Miyaura Cross-Coupling of Arylboronic Acids and α-Iminonitriles through C–CN Bond Activation
A Pd-catalyzed Suzuki–Miyaura cross-coupling reaction between arylboronic acids and α-iminonitriles has been developed. The reaction proceeds through selective activation of the C–CN bond, tolerates a wide range of substituents, and delivers the versatile ketone products in moderate to excellent yields.
Liu, Kui,Tao, Shou-Wei,Qian, Chun,Zhu, Yong-Ming
supporting information
p. 4769 - 4775
(2018/09/06)

Kumada Arylation of Secondary Amides Enabled by Chromium Catalysis for Unsymmetric Ketone Synthesis under Mild Conditions
The synthesis of aromatic ketones by chromium-catalyzed Kumada arylation of secondary amides with organomagnesium reagents is described. This reaction was enabled by using low-cost chromium(III) salt as a precatalyst, combined with trimethylsilyl chloride
Chen, Changpeng,Liu, Pei,Luo, Meiming,Zeng, Xiaoming
p. 5864 - 5868
(2018/05/29)

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)

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)

Revealing the Structure and Reactivity of the Active Species in the FeCl2-TBHP System: Case Study on Alkene Oxidation
A mechanism involving a quintet ferryl [FeIV=O] species has been disclosed for the oxidation of alkene under the FeCl2-TBHP system. Both theoretical and experimental results suggested that the quintet ferryl species [FeIV=O] was produced by the reaction of FeCl2 with TBHP. A Mulliken atomic spin density distribution on [FeIV=O] showed that the O site has strong radical character and could easily react with alkene to form a carbon radical intermediate. This radical could be further oxidized by TBHP to lead to the C=C bond cleavage of alkene.
Huang, Zhiliang,Qi, Xiaotian,Lee, Jyh-Fu,Lei, Aiwen
supporting information
p. 1635 - 1640
(2018/06/11)

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)

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)

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
p. 6510 - 6513
(2017/12/26)

Palladium-catalyzed Suzuki-Miyaura coupling of aryl esters
The Suzuki-Miyaura coupling is among the most important C-C bond-forming reactions available due to its reliability, chemoselectivity, and diversity. Aryl halides and pseudohalides such as iodides, bromides, and triflates are traditionally used as the electrophilic coupling partner. The expansion of the reaction scope to nontraditional electrophiles is an ongoing challenge to enable an even greater number of useful products to be made from simple starting materials. Herein, we present how an NHC-based Pd catalyst can enable Suzuki-Miyaura coupling where the C(acyl)-0 bond of aryl esters takes on the role of electrophile, allowing the synthesis of various ketone-containing products. This contrasts known reactions of similar esters that provide biaryls via nickel catalysis. The underlying cause of this mechanistic divergence is investigated by DFT calculations, and the robustness of esters compared to more electrophilic acylative coupling partners is analyzed.
Halima, Taoufik Ben,Zhang, Wanying,Yalaoui, Imane,Hong, Xin,Yang, Yun-Fang,Houk, Kendall N.,Newman, Stephen G.
p. 1311 - 1318
(2017/05/16)

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)

Ni-Catalyzed cross-coupling reactions of N-acylpyrrole-type amides with organoboron reagents
The catalytic conversion of amides to ketones is highly desirable yet challenging in organic synthesis. We herein report the first Ni/bis-NHC-catalyzed cross-coupling of N-acylpyrrole-type amides with arylboronic esters to obtain diarylketones. This method is facilitated by a new chelating bis-NHC ligand. The reaction tolerates diverse functional groups on both arylamide and arylboronic ester partners including sensitive ester and ketone groups.
Huang, Pei-Qiang,Chen, Hang
p. 12584 - 12587
(2017/11/30)

Palladium Catalyzed Carbonylative Coupling for Synthesis of Arylketones and Arylesters Using Chloroform as the Carbon Monoxide Source
We describe a modular, palladium catalyzed synthesis of aryl(hetero)aryl benzophenones and aryl benzoates from aryl(hetero)aryl halides using CHCl3 as the carbonyl source in the presence of KOH. The reaction occurs in tandem through an initial carbonylation to generate an aroyl halide, which undergoes coupling with arylboronic acids, bornonates, and phenols. Direct carbonylative coupling of indoles at the third position has also been accomplished under slightly modified reaction conditions by in situ activation of the C-H bond. Notably, CHCl3 is a convenient and safe alternation of CO gas, provides milder reaction conditions with high functional group tolerance, and gives the products in moderate to good yields.
Sharma, Poonam,Rohilla, Sandeep,Jain, Nidhi
p. 1105 - 1113
(2018/06/18)