- Mechanochemical Solvent-Free Suzuki–Miyaura Cross-Coupling of Amides via Highly Chemoselective N?C Cleavage
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Although cross-coupling reactions of amides by selective N?C cleavage are one of the most powerful and burgeoning areas in organic synthesis due to the ubiquity of amide bonds, the development of mechanochemical, solid-state methods remains a major challe
- Ma, Yangmin,Shao, Lei,Szostak, Michal,Wang, Ruihong,Zhang, Jin,Zhang, Pei
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supporting information
(2022/01/04)
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- Suzuki-Miyaura cross-coupling of esters by selective O-C(O) cleavage mediated by air- And moisture-stable [Pd(NHC)(μ-Cl)Cl]2precatalysts: Catalyst evaluation and mechanism
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The cross-coupling of aryl esters has emerged as a powerful platform for the functionalization of otherwise inert acyl C-O bonds in chemical synthesis and catalysis. Herein, we report a combined experimental and computational study on the acyl Suzuki-Miyaura cross-coupling of aryl esters mediated by well-defined, air- and moisture-stable Pd(ii)-NHC precatalysts [Pd(NHC)(μ-Cl)Cl]2. We present a comprehensive evaluation of [Pd(NHC)(μ-Cl)Cl]2 precatalysts and compare them with the present state-of-the-art [(Pd(NHC)allyl] precatalysts bearing allyl-type throw-away ligands. Most importantly, the study reveals [Pd(NHC)(μ-Cl)Cl]2 as the most reactive precatalysts discovered to date in this reactivity manifold. The unique synthetic utility of this unconventional O-C(O) cross-coupling is highlighted in the late-stage functionalization of pharmaceuticals and sequential chemoselective cross-coupling, providing access to valuable ketone products by a catalytic mechanism involving Pd insertion into the aryl ester bond. Furthermore, we present a comprehensive study of the catalytic cycle by DFT methods. Considering the clear advantages of [Pd(NHC)(μ-Cl)Cl]2 precatalysts on several levels, including facile one-pot synthesis, superior atom-economic profile to all other Pd(ii)-NHC catalysts, and versatile reactivity, these should be considered as the 'first-choice' catalysts for all routine applications in ester O-C(O) bond activation.
- Cavallo, Luigi,Nolan, Steven P.,Poater, Albert,Szostak, Michal,Yang, Shiyi,Zhou, Tongliang
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p. 3189 - 3197
(2021/05/25)
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- Poly(ethylene glycol) dimethyl ether mediated oxidative scission of aromatic olefins to carbonyl compounds by molecular oxygen
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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
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p. 13848 - 13852
(2021/04/22)
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- Silylcarboxylic Acids as Bifunctional Reagents: Application in Palladium-Catalyzed External-CO-Free Carbonylative Cross-Coupling Reactions
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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
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supporting information
p. 4078 - 4083
(2020/07/30)
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- N-Acylcarbazoles and N-Acylindoles: Electronically Activated Amides for N-C(O) Cross-Coupling by Nlpto Ar Conjugation Switch
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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
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supporting information
p. 4703 - 4709
(2020/06/17)
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- N-Acyl-5,5-Dimethylhydantoins: Mild Acyl-Transfer Reagents for the Synthesis of Ketones Using Pd-PEPPSI or Pd/Phosphine Catalysts
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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
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p. 1043 - 1051
(2020/07/15)
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- Suzuki-Miyaura Cross-Coupling of Amides using Well-Defined, Air-Stable [(PR3)2Pd(II)X2] Precatalysts
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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
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supporting information
(2020/05/26)
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- Synthesis of biaryl ketones by arylation of Weinreb amides with functionalized Grignard reagents under thermodynamic controlvs.kinetic control ofN,N-Boc2-amides
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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
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supporting information
p. 3827 - 3831
(2020/06/03)
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- Kinetically Controlled, Highly Chemoselective Acylation of Functionalized Grignard Reagents with Amides by N?C Cleavage
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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
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supporting information
p. 611 - 615
(2020/01/02)
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- Chemoselective Synthesis of Aryl Ketones from Amides and Grignard Reagents via C(O)-N Bond Cleavage under Catalyst-Free Conditions
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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
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p. 11823 - 11838
(2019/10/02)
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- Well-Defined, Air-Stable, and Readily Available Precatalysts for Suzuki and Buchwald-Hartwig Cross-coupling (Transamidation) of Amides and Esters by N-C/O-C Activation
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A general class of well-defined, air-stable, and readily available Pd(II)-NHC precatalysts (NHC = N-heterocyclic carbene) for Suzuki and Buchwald-Hartwig cross-coupling of amides (transamidation) and esters by selective N-C/O-C cleavage is reported. Since these precatalysts are highly active and the easiest to synthesize, the study clearly suggests that [Pd(NHC)(acac)Cl] should be routinely included during the development of new cross-coupling methods. An assay for in situ screening of NHC salts in this cross-coupling manifold is presented.
- Zhou, Tongliang,Li, Guangchen,Nolan, Steven P.,Szostak, Michal
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supporting information
p. 3304 - 3309
(2019/05/10)
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- Ligand-free Palladium-Catalyzed Carbonylative Suzuki Coupling of Aryl Iodides in Aqueous CH3CN with Sub-stoichiometric Amount of Mo(CO)6 as CO Source
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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
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p. 2117 - 2123
(2019/03/28)
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- Sequential Organozinc Formation and Negishi Cross-Coupling of Amides Catalysed by Cobalt Salt
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Herein, a cobalt-catalysed Negishi-type cross-coupling of amide derivatives is described. Apart from being the first example of cobalt-catalysed Negishi-type coupling of amides, the process described employs a unique, simple, and cheap catalytic system to perform both the organozinc formation and the Negishi-type coupling. Indeed, the same cobalt(II) bromide salt used to form the arylzinc species from aryl bromides is then re-used to perform the cross coupling of this resulting arylzinc with N-benzoyl glutarimides at room temperature. The main advantages of the reaction presented are its robustness and ease of use. Indeed, the reactions of organozinc formation and Negishi-type coupling are performed without precautions toward water or oxygen. (Figure presented.).
- Dorval, Céline,Dubois, Elodie,Bourne-Branchu, Yann,Gosmini, Corinne,Danoun, Grégory
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supporting information
p. 1777 - 1780
(2019/02/26)
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- Triflamides: Highly Reactive, Electronically Activated N-Sulfonyl Amides in Catalytic N-C(O) Amide Cross-Coupling
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The direct, highly chemoselective Suzuki-Miyaura cross-coupling of trifluoromethanesulfonamides (triflamides) by selective N-C(O) amide bond cleavage is reported. This operationally simple, mild, and user-friendly method accomplishes the direct synthesis of ketones from amides by a catalytic manifold as a powerful alternative to Weinreb amides. Mechanistic studies support rotational inversion and electronic activation, favoring selective insertion under mild conditions. Our data strongly suggest that triflamides should be routinely considered as precursors in amide bond cross-coupling.
- Shi, Shicheng,Lalancette, Roger,Szostak, Roman,Szostak, Michal
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supporting information
p. 1253 - 1257
(2019/02/26)
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- Transition-metal-free carbonylation of aryl halides with arylboronic acids by utilizing stoichiometric CHCl3 as the carbon monoxide-precursor
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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
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supporting information
p. 2911 - 2915
(2019/06/18)
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- Flow hydrodediazoniation of aromatic heterocycles
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Continuous flow processing was applied for the rapid replacement of an aromatic amino group with a hydride. The approach was applied to a range of aromatic heterocycles, confirming the wide scope and substituent-tolerance of the processes. Flow equipment was utilized and the process optimised to overcome the problematically-unstable intermediates that have restricted yields in previous studies relying on batch procedures. Various common organic solvents were investigated as potential hydride sources. The approach has allowed key structures, such as amino-pyrazoles and aminopyridines, to be deaminated in good yield using a purely organic-soluble system.
- R?der, Liesa,Nicholls, Alexander J.,Baxendale, Ian R.
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- N-heterocyclic carbene palladium(II)-catalyzed Suzuki-Miyaura cross coupling of N-acylsuccinimides by C-N cleavage
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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
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- N-Acyl-5,5-dimethylhydantoin, a New Mild Acyl-Transfer Reagent in Pd Catalysis: Highly Efficient Synthesis of Functionalized Ketones
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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
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p. 1188 - 1199
(2018/09/06)
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- Acyl and Decarbonylative Suzuki Coupling of N-Acetyl Amides: Electronic Tuning of Twisted, Acyclic Amides in Catalytic Carbon-Nitrogen Bond Cleavage
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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
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p. 9131 - 9139
(2018/09/21)
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- N-Acylsuccinimides: Efficient acylative coupling reagents in palladium-catalyzed Suzuki coupling via C–N cleavage
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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
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supporting information
p. 3819 - 3822
(2017/09/15)
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- Palladium Catalyzed Carbonylative Coupling for Synthesis of Arylketones and Arylesters Using Chloroform as the Carbon Monoxide Source
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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
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p. 1105 - 1113
(2018/06/18)
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- General Method for the Suzuki-Miyaura Cross-Coupling of Primary Amide-Derived Electrophiles Enabled by [Pd(NHC)(cin)Cl] at Room Temperature
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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
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p. 6510 - 6513
(2017/12/26)
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- N-Methylamino Pyrimidyl Amides (MAPA): Highly Reactive, Electronically-Activated Amides in Catalytic N-C(O) Cleavage
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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
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supporting information
p. 4656 - 4659
(2017/09/12)
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- The second aryl ketone compounds
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The invention provides a synthetic method for diaryl ketone compounds. The method comprises the following steps: adding ester derivatives of raw material diaryl methanol, DDQ and water into an organic solvent, carrying out stirring, then carrying out heating to 110 to 140 DEG C and carrying out reaction for 0.5 to 12 h, and subjecting obtained reaction liquid to after-treatment so as to obtain the diaryl ketone compounds, wherein the ester derivatives of the raw material diaryl methanol have a structural formula as shown in a formula (V), (VI), (VII) or (VIII), and one-to-one correspondingly obtained products have the structural formula as shown in the formula (I), (II), (III) or (IV). The synthetic method for the diaryl ketone compounds provided by the invention has the advantages of simple, convenient and safe operation, mild reaction conditions and high product selectivity.
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Paragraph 0081; 0082
(2017/08/24)
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- Synthesis and structural characterization of Pd(II) thiosemicarbazonato complex: Catalytic evaluation in synthesis of diaryl ketones from aryl aldehydes and arylboronic acids
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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
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supporting information
p. 405 - 409
(2017/01/10)
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- Transition metal-free Suzuki type cross-coupling reaction for the synthesis of dissymmetric ketones
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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
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supporting information
p. 3201 - 3204
(2017/07/27)
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- Suzuki Coupling of Amides via Palladium-Catalyzed C–N Cleavage of N-Acylsaccharins
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A palladium-catalyzed cross-coupling of activated amides with arylboronic acids has been developed via C–N bond cleavage. This approach demonstrated high tolerance to a variety of alkyl, aryl, heterocyclic and vinyl substituents. Unsymmetrical ketones could be achieved in excellent yield under mild conditions with 1% catalyst loadings. (Figure presented.).
- Wu, Hongxiang,Li, Yue,Cui, Ming,Jian, Junsheng,Zeng, Zhuo
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p. 3876 - 3880
(2016/12/16)
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- N-acylsaccharins: Stable electrophilic amide-based acyl transfer reagents in Pd-catalyzed Suzuki-Miyaura coupling via N-C cleavage
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The development of efficient catalytic methods for N-C bond cleavage in amides remains an important synthetic challenge. The first Pd-catalyzed Suzuki-Miyaura cross-coupling of N-acylsaccharins with boronic acids by selective N-C bond activation is reported. The reaction enables preparation of a variety of functionalized diaryl and alkyl-aryl ketones with broad functional group tolerance and in good to excellent yields. Of general interest, N-acylsaccharins serve as new, highly reactive, bench-stable, economical, amide-based, electrophilic acyl transfer reagents via acyl-metal intermediates. Mechanistic studies strongly support the amide N-C(O) bond twist as the enabling feature of N-acylsaccharins in the N-C bond cleavage.
- Liu, Chengwei,Meng, Guangrong,Liu, Yongmei,Liu, Ruzhang,Lalancette, Roger,Szostak, Roman,Szostak, Michal
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supporting information
p. 4194 - 4197
(2016/09/09)
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- Diaryl a ketone compound catalytic oxidation synthesis method
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The invention provides a catalytic oxidation synthesis method of a diaryl ketone compound. In an organic solvent, ester derivatives of diaryl methanol are used as reaction substrates, DDQ and TBN are used as catalysts, oxygen is used as an oxidant, so as to react for 1 to 12 h under the conditions of oxygen pressure of 0.1 to 0.4 MPa and temperature of 110 to 140 DEG C, and post processing is performed on reaction liquid, so as to obtain a product of the diaryl ketone compound; structural formulas of the ester derivatives of the diaryl methanol as the reaction substrates are shown in the formulas (V), (VI), (VII) or (VIII), and structural formulas of products which are correspondingly obtained one by one are shown in the formulas (I), (II), (III) or (IV). The catalytic oxidation synthesis method has the advantages of simplicity, convenience and safety in operation, mild reaction condition, high product selectivity and environmental friendliness.
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Paragraph 0083-0084
(2020/05/05)
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- Coupling of aromatic aldehydes with aryl halides in the presence of nickel catalysts with diazabutadiene ligands
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Nickel catalysts with diazabutadiene ligands promote cross-coupling of benzaldehydes with aryl halides in the presence of zinc as reducing agent, which leads to the corresponding benzhydrols and benzophenones. The benzophenone percentage considerably increases when lithium chloride additive is used.
- Asachenko,Valaeva,Kudakina,Uborsky,Izmer,Kononovich,Voskoboynikov
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p. 456 - 463
(2017/03/08)
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- Microwave Heated Continuous Flow Palladium(II)-Catalyzed Desulfitative Synthesis of Aryl Ketones
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A protocol for Pd(II)-catalyzed desulfitative synthesis of aryl ketones from sodium aryl sulfinates and nitriles in continuous flow has been developed. The reactions proceed with microwave heating using microwave transparent tube reactors, affording the desired aryl ketones in fair to good yields. Microwave transparent aluminum oxide reactors were identified as a safe and thermostable alternative to borosilicate glass reactors.
- Skillinghaug, Bobo,Rydfjord, Jonas,S?vmarker, Jonas,Larhed, Mats
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supporting information
p. 2005 - 2011
(2017/02/10)
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- Nickel-catalyzed diaryl ketone synthesis by N-C cleavage: Direct negishi cross-coupling of primary amides by site-selective N,N-Di-boc activation
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A general Negishi acylation of primary amides enabled by a combination of site-selective N,N-di-Boc activation and nickel catalysis is reported for the first time. The reaction is promoted by a bench-stable, inexpensive Ni catalyst. The reaction shows excellent functional group compatibility, affording functionalized diaryl ketones by selective N-C cleavage. Most notably, this protocol represents the first amide cross-coupling by direct metal insertion of simple and readily available primary amides. The overall strategy by N,N-di-Boc activation/metal insertion is suitable for a broad range of coupling protocols via acylmetals. Mechanistic experiments suggest high reactivity of N,N-di-Boc activated 1° amides in direct amide C-N cross-couplings.
- Shi, Shicheng,Szostak, Michal
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p. 5872 - 5875
(2016/11/29)
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- Iron-catalyzed carbonylation of aryl halides with arylborons using stoichiometric chloroform as the carbon monoxide source
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A general iron-catalyzed carbonylative Suzuki-Miyaura coupling of aryl halides with arylborons is reported, using stoichiometric CHCl3 as the CO source. The high efficiency, economy, selectivity, and operational simplicity of this transformation make this method a valuable tool in organic synthesis. Importantly, the presented strategy allows effective 13C labeling simply by using the commercially available 13C-labeled CHCl3. On the basis of the initial mechanistic exploration, an aryl radical intermediate is proposed in the present carbonylation process.
- Zhao, Hongyuan,Du, Hongyan,Yuan, Xiaorong,Wang, Tianjiao,Han, Wei
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supporting information
p. 5782 - 5787
(2016/11/06)
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- Efficient Synthesis of Diaryl Ketones by Nickel-Catalyzed Negishi Cross-Coupling of Amides by Carbon–Nitrogen Bond Cleavage at Room Temperature Accelerated by a Solvent Effect
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The first Negishi cross-coupling of amides for the synthesis of versatile diaryl ketones by selective C?N bond activation under exceedingly mild conditions is reported. The cross-coupling was accomplished with bench-stable, inexpensive precatalyst [Ni(PPh3)2Cl2] that shows high functional-group tolerance and enables the synthesis of highly functionalized diaryl ketone motifs. The coupling occurred with excellent chemoselectivity favoring the ketone (cf. biaryl) products. Notably, this process represents the mildest conditions for amide N?C bond activation accomplished to date (room temperature, 10 min). Considering the versatile role of polyfunctional biaryl ketone linchpins in modern organic synthesis, availability, and excellent functional-group tolerance of organozinc reagents, this strategy provides a new platform for amide N?C bond/organozinc cross-coupling under mild conditions.
- Shi, Shicheng,Szostak, Michal
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p. 10420 - 10424
(2016/07/21)
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- Palladium-catalyzed Suzuki-Miyaura coupling of amides by carbon-nitrogen cleavage: General strategy for amide N-C bond activation
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The first palladium-catalyzed Suzuki-Miyaura cross-coupling of amides with boronic acids for the synthesis of ketones by sterically-controlled N-C bond activation is reported. The transformation is characterized by operational simplicity using bench-stable, commercial reagents and catalysts, and a broad substrate scope, including substrates with electron-donating and withdrawing groups on both coupling partners, steric-hindrance, heterocycles, halides, esters and ketones. The scope and limitations are presented in the synthesis of >60 functionalized ketones. Mechanistic studies provide insight into the catalytic cycle of the cross-coupling, including the first experimental evidence for Pd insertion into the amide N-C bond. The synthetic utility is showcased by a gram-scale cross-coupling and cross-coupling at room temperature. Most importantly, this process provides a blueprint for the development of a plethora of metal catalyzed reactions of typically inert amide bonds via acyl-metal intermediates. A unified strategy for amide bond activation to enable metal insertion into N-C amide bond is outlined (Scheme 1).
- Meng, Guangrong,Szostak, Michal
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supporting information
p. 5690 - 5707
(2016/07/06)
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- An unusual chemoselective oxidation strategy by an unprecedented exploration of an electrophilic center of DMSO: A new facet to classical DMSO oxidation
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A conceptually new dimethyl sulfoxide (DMSO) based oxidation process without the use of any activator has been demonstrated for the oxidation of active methylenes and benzhydrols. The developed protocol utilizes the electrophilic center of DMSO for oxidation, which was unexplored before. Mechanistic investigation has confirmed that the source of oxygen is DMSO.
- Chebolu, Rajesh,Bahuguna, Ashish,Sharma, Reena,Mishra, Vivek Kumar,Ravikumar
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p. 15438 - 15441
(2015/10/20)
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- A Convenient Palladium-Catalyzed Carbonylative Suzuki Coupling of Aryl Halides with Formic Acid as the Carbon Monoxide Source
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A practical palladium-catalyzed carbonylative Suzuki coupling of aryl halides under carbon monoxide gas-free conditions has been developed. Here, formic acid was utilized as the carbon monoxide source for the first time with acetic anhydride as the additive. A variety of diarylketones were produced in moderate to excellent yields from the corresponding aryl halides and arylboronic acids.
- Qi, Xinxin,Jiang, Li-Bing,Li, Hao-Peng,Wu, Xiao-Feng
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supporting information
p. 17650 - 17656
(2015/12/05)
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- DDQ/tert-Butyl nitrite-catalyzed aerobic oxidation of diarylmethane sp3 C-H bonds
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An efficient 2,3-dichloro-5,6-dicyano-1,4-benzoquinone/tert-butyl nitrite-catalyzed aerobic oxidation of diarylmethane sp3 C-H bonds in the presence of acetic acid has been developed. Under the optimal reaction conditions, a number of diarylmethanes can be directly converted to their corresponding diarylketones in good to excellent yields. In addition, a plausible reaction mechanism has been investigated.
- Ma, Jiaqi,Hu, Zhiming,Li, Meichao,Zhao, Weijuan,Hu, Xinquan,Mo, Weimin,Hu, Baoxiang,Sun, Nan,Shen, Zhenlu
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p. 6733 - 6739
(2015/08/24)
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- Transition-metal-free, ambient-pressure carbonylative cross-coupling reactions of aryl halides with potassium aryltrifluoroborates
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We disclose an unprecedented transition-metal-free carbonylative cross coupling of aryl halides with potassium aryl trifluoroborates even at atmospheric pressure of carbon monoxide. This protocol is efficient, operationally simple, and shows wide scope with regard to both aryl halides and potassium aryl trifluoroborates containing a series of active functional groups.
- Jin, Fengli,Han, Wei
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supporting information
p. 9133 - 9136
(2015/06/08)
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- Palladacycle-Catalyzed Carbonylative Suzuki-Miyaura Coupling with High Turnover Number and Turnover Frequency
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This work reports the carbonylative Suzuki-Miyaura coupling of aryl iodides catalyzed by palladacycles. More importantly, the palladacycles have been used to generate high turnover numbers (TON's) and turnover frequencies (TOF's). A range of aryl iodides can be coupled with arylboronic acids, generating TON's in the range of 106 to 107 and TOF's in the range of 105 to 106 h-1. Comparison of the palladacycles with a conventional palladium source shows their superiority in generating high TON's and TOF's.
- Gautam, Prashant,Bhanage, Bhalchandra M.
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p. 7810 - 7815
(2015/08/18)
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- Nickel-catalyzed cross-coupling of carboxylic anhydrides with arylboronic acids
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A nickel-based catalyst was employed in the cross-coupling of carboxylic anhydrides with arylboronic acids, and the reaction was carried out under mild conditions. This new protocol provides an efficient, cheap and convenient alternative to synthesizing aromatic ketones.
- Chen, Qiang,Fan, Xin-Heng,Zhang, Li-Peng,Yang, Lian-Ming
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p. 53885 - 53890
(2015/01/16)
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- Tandem nucleophilic addition-Oppenauer oxidation of aromatic aldehydes to aryl ketones with triorganoaluminium reagents
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In the presence of pinacolone, the in situ prepared triorganoaluminium reagents reacted with aromatic aldehydes to give ketones in moderate to high yield. We propose that the products are formed via a tandem organoaluminium reagents addition-Oppenauer oxidation sequence. The Royal Society of Chemistry 2013.
- Fu, Ying,Yang, Yanshou,Hügel, Helmut M.,Du, Zhengyin,Wang, Kehu,Huang, Danfeng,Hu, Yulai
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supporting information
p. 4429 - 4432
(2013/08/23)
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- Efficient, recyclable and phosphine-free carbonylative Suzuki coupling reaction using immobilized palladium ion-containing ionic liquid: Synthesis of aryl ketones and heteroaryl ketones
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The carbonylative Suzuki coupling reaction of aryl and heteroaryl iodides was studied by using immobilized palladium ion-containing ionic liquid (ImmPd-IL). The protocol was optimized with respect to various reaction parameters, applied to a wide variety of substituted aryl/heteroaryl iodides and various aryl/heteroaryl boronic acids with different steric and electronic properties, and afforded the corresponding products in good to excellent yield. This is an efficient, heterogeneous catalyst which avoids the use of phosphine ligands, and its reusability was tested in up to four consecutive cycles. The recycled catalyst was characterized by using XPS analysis.
- Khedkar, Mayur V.,Sasaki, Takehiko,Bhanage, Bhalchandra M.
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p. 7791 - 7797
(2013/06/27)
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- Development of decarboxylative coupling processes for the synthesis of azomethines and ketones
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A bimetallic catalyst system has been developed that allows the synthesis of azomethines by a one-pot three-component decarboxylative coupling, starting from simple, nontoxic precursors, i.e. potassium α-oxo carboxylates, aryl halides and primary amines. In the presence of 15 mol-% copper/phenanthroline and 1 mol-% Pd/dppf, a wide range of valuable imines is conveniently accessible in high yields at 100 °C, an unprecedentedly low temperature for redox-neutral decarboxylative cross-coupling reactions. Hydrogenation of the azomethine products leads to secondary amines. Alternatively, they can be hydrolyzed in situ to aryl ketones. The resulting ketone synthesis via azomethine intermediates is also of interest as it gives higher yields at much lower temperatures than the direct decarboxylative coupling of α-oxo carboxylates with aryl halides. A convenient synthesis of azomethines by a one-pot three-component decarboxylative coupling, starting from potassium α-oxo carboxylates, aryl halides and primary amines is described. Combined with in situ hydrolysis, ketones are obtained. Thisamine-mediated ketone synthesis gives higher yields at lower temperatures than the direct coupling of α-oxo carboxylates. Copyright
- Collet, Florence,Song, Bingrui,Rudolphi, Felix,Goossen, Lukas J.
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experimental part
p. 6486 - 6501
(2011/12/05)
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- Reversed-polarity synthesis of diaryl ketones via palladium-catalyzed cross-coupling of acylsilanes
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Acylsilanes serve as acyl anion equivalents in a palladium-catalyzed cross-coupling reaction with aryl bromides to give unsymmetrical diaryl ketones. Water plays a unique and crucial activating role in these reactions. High-throughput experimentation techniques provided successful reaction conditions initially involving phosphites as ligands. Ultimately, 1,3,5,7-tetramethyl-6-phenyl-2,4,8-trioxa-6-phosphaadamantane was identified as giving a longer-lived catalyst with higher turnover numbers. Its use, in conjunction with a palladacycle precatalyst, led to optimal reaction rates and yields. Scope and limitations of this novel method are presented along with initial mechanistic insight.
- Schmink, Jason R.,Krska, Shane W.
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p. 19574 - 19577
(2012/01/13)
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- Ligand-free Pd-catalyzed carbonylative cross-coupling reactions under atmospheric pressure of carbon monoxide: Synthesis of aryl ketones and heteroaromatic ketones
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The carbonylative Suzuki cross-coupling reactions of boronic acids with aryl iodides catalyzed by Pd2(dba)3 as a ligand-free catalyst under atmospheric pressure of carbon monoxide has been firstly developed. Under mild reaction conditions, a broad range of aryl/heteroaryl iodides and aryl/heteroaryl boronic acids were selectively coupled to afford the corresponding diaryl ketones in good to excellent yields at low catalyst loadings (0.05 to 2 mol-%). Moreover, the catalyst can also be recycled. The carbonylative Suzuki cross-coupling reactions of boronic acids with aryl iodides catalyzed by Pd2(dba)3 as a ligand-free catalyst under an atmosphere of carbon monoxide has been developed. A broad range of aryl/heteroaryl iodides and aryl/heteroaryl boronic acids were selectively coupled to afford the corresponding diaryl ketones in good to excellent yields. The catalyst can also be recycled.
- Li, Hongling,Yang, Min,Qi, Yanxing,Xue, Jijun
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supporting information; experimental part
p. 2662 - 2667
(2011/06/25)
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- Preparation of aryl ketones via Ni-catalyzed Negishi-coupling reactions with acid chlorides
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A Ni-catalyst-catalyzed cross-coupling reaction of organozinc reagents with acid chlorides has been successfully developed. Mild reaction conditions were required to complete the coupling reactions affording the corresponding aryl ketones in good to excellent yields.
- Kim, Seung-Hoi,Rieke, Reuben D.
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experimental part
p. 1523 - 1526
(2011/05/16)
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- Intermolecular N-heterocyclic carbene catalyzed hydroacylation of arynes
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A formal introduction: The conceptually new N-heterocyclic carbene catalyzed formal insertion of arynes into the Cformyl-H bond of aldehydes demonstrates the compatibility of nucleophilic NHCs with electrophilic arynes. This NHC-catalyzed hydroacylation of arynes allows the conversion of aliphatic, α,β-unsaturated, and aromatic aldehydes into aryl ketones; 27 examples and a preliminary mechanistic investigation are provided. Copyright
- Biju, Akkattu T.,Glorius, Frank
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supporting information; experimental part
p. 9761 - 9764
(2011/03/16)
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- PROCESS FOR PREPARING KETONES FROM ALPHA-OXO CARBOXYLATES AND ARYL BROMIDES
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A process for preparing ketones of the general formula (III) where R is an optionally substituted carbocyclic aromatic radical having 6 to 24 carbon atoms or an optionally substituted alkyl radical or an optionally substituted heteroaromatic radical having 5 to 24 carbon atoms, andR1 is an optionally substituted carbocyclic aromatic radical having 6 to 24 carbon atoms or an optionally substituted heteroaromatic radical having 5 to 24 carbon atoms, by reacting alpha-oxo carboxylates of the general formula (I) wherein n and m is a number in the range from 1 to 6, M(m+) is a cation, and R has the meaning indicated for formula (III), with aryl bromides of the general formula (II) [in-line-formulae]R1—Br ??(II)[/in-line-formulae] where R1 has the meaning indicated for formula (III), in the presence of two transition metals or compounds thereof as catalyst, is described.
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Page/Page column 3-4
(2009/09/08)
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- Synthesis of ketones from α-oxocarboxylates and aryl bromides by Cu/Pd-catalyzed decarboxylative cross-coupling
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(Chemical Equation Presented) The power of two metals: A Pd/Cu catalyst system mediates the in situ formation of acyl nucleophiles by decarboxylation of readily accessible and stable salts of α-oxocarboxylic acids and their cross-coupling with aryl or heteroaryl bromides to give ketones. The reaction may be usedin the presence of many functional groups and provides good yields.
- Goossen, Lukas J.,Rudolphi, Felix,Oppel, Christoph,Rodriguez, Nuria
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p. 3043 - 3045
(2008/12/23)
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