- Pd-Catalysed carbonylative Suzuki-Miyaura cross-couplings using Fe(CO)5under mild conditions: generation of a highly active, recyclable and scalable ‘Pd-Fe’ nanocatalyst
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The dual function and role of iron(0) pentacarbonyl [Fe(CO)5] has been identified in gaseous CO-free carbonylative Suzuki-Miyaura cross-couplings, in which Fe(CO)5supplied COin situ, leading to the propagation of catalytically active Pd-Fe nanoparticles. Compared with typical carbonylative reaction conditions, CO gas (at high pressures), specialised exogenous ligands and inert reaction conditions were avoided. Our developed reaction conditions are mild, do not require specialised CO high pressure equipment, and exhibit wide functional group tolerance, giving a library of biaryl ketones in good yields.
- Zhu, Zhuangli,Wang, Zhenhua,Jian, Yajun,Sun, Huaming,Zhang, Guofang,Lynam, Jason M.,McElroy, C. Robert,Burden, Thomas J.,Inight, Rebecca L.,Fairlamb, Ian J. S.,Zhang, Weiqiang,Gao, Ziwei
-
supporting information
p. 920 - 926
(2021/02/09)
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- Synthesis, structure, and characterization of picolyl- and benzyl-linked biphenyl palladium N-heterocyclic carbene complexes and their catalytic activity in acylative cross-coupling reactions
-
N-heterocyclic carbene ligands with picolyl (L1H2Br2, L3H2Br2) and benzyl (L2H2Br2, L4H2Br2) linked biphenyl backbone were synthesized and characterized. Their palladium(II) complexes [PdL1]Br2 (1), [PdL2Br2] (2), [PdL3]Br2 (3), and [PdL4Br2] (4) were synthesized by direct method using Pd(OAc)2. All complexes (1–4) were characterized by CHN analysis, electrospray ionization-MS, nuclear magnetic resonance, and single-crystal X-ray diffraction. Molecular structures confirm the distorted square planar geometry around the Pd(II) center. All of them showed good catalytic activity in acylative Suzuki cross coupling of phenyl boronic acid with benzoyl chloride to afford benzophenone in good yields.
- Muniyappan, Nalluchamy,Sabiah, Shahulhameed
-
-
- NITRATION
-
The present invention relates to a process for preparing a nitrated compound, comprising the step of reacting a compound (A) comprising at least one substituted or unsubstituted aromatic or heteroaromatic ring, wherein said heteroaromatic ring comprises at least one heteroatom selected from the group consisting of oxygen, sulfur, phosphor, selenium and nitrogen, with a compound of formula (I) wherein Y is selected from the group consisting of hydrogen and nitro.
- -
-
Page/Page column 36; 38; 43; 52-53; 68; 69
(2020/05/28)
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- 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
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supporting information
(2020/11/03)
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- Xantphos-ligated palladium dithiolates: An unprecedented and convenient catalyst for the carbonylative Suzuki–Miyaura cross-coupling reaction with high turnover number and turnover frequency
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Xantphos- and dithiolate-ligated macrocyclic palladium complexes as an efficient and stable catalyst for the carbonylative Suzuki–Miyaura cross-coupling reaction have been synthesized. The catalysts were characterized by 1H-nuclear magnetic resonance (NMR), CHNS (carbon, hydrogen, nitrogen, and sulfur) analysis, melting point analysis, and 31P-NMR spectroscopy. Several sensitive functional groups (e.g., –NO2, –F, –Cl, –Br, –NH2, and –CN) on the aromatic ring were well tolerated in the carbonylative Suzuki–Miyaura coupling reaction. The present palladium complexes produce six times higher turnover number (TON) and five times higher turnover frequency (TOF) compared with conventional homogeneous palladium precursors. Maximum TONs in the range of 105 to 106 and TOF in the range of 104 to 105 could be generated by a very low amount of catalyst loading (10–5?mol%).
- Gaikwad, Vinayak V.,Mane, Pravin A.,Dey, Sandip,Bhanage, Bhalchandra M.
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- Solvent-free, microwave assisted oxidation of alcohols with 4-hydroxypyridinium chlorochromate functionalized silica gel
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4-Hydroxypyridinium chlorochromate functionalized silica gel was found to be an efficient and reusable oxidant for the very fast oxidation of primary and secondary alcohols to the corresponding carbonyl compounds under solventfree conditions and microwave irradiation in excellent yields.
- AHMADI, Sayed Ali,GHALEHBANDI, Shermineh Sadat,GHAZANFARI, Dadkhoda,SHEIKHHOSSEINI, Enayatollah
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p. 283 - 289
(2020/10/06)
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- Heterogeneous Suzuki-Miyaura coupling of heteroaryl ester: Via chemoselective C(acyl)-O bond activation
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A site-selective supported palladium nanoparticle catalyzed Suzuki-Miyaura cross-coupling reaction with heteroaryl esters and arylboronic acids as coupling partners was developed. This methodology provides a heterogeneous catalytic route for aryl ketone formation via C(acyl)-O bond activation of esters by successful suppression of the undesired decarbonylation phenomenon. The catalyst can be reused and shows high activity after eight cycles. The XPS analysis of the catalyst before and after the reaction suggested that the reaction might be performed via a Pd0/PdII catalytic cycle that began with Pd0.
- Ma, Hongpeng,Bai, Chaolumen,Bao, Yong-Sheng
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p. 17266 - 17272
(2019/06/24)
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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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- Palladium-Catalyzed Direct Oxidative Coupling of Iodoarenes with Primary Alcohols Leading to Ketones: Application to the Synthesis of Benzofuranones and Indenones
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In the present study, a palladium-catalyzed direct oxidative acylation through cross-dehydrogenative coupling has been investigated, utilizing readily available primary alcohols as acylating sources. Overall, this oxidative coupling proceeds via three distinct transformations such as oxidation, radical formation, and cross-coupling in one catalytic process. This protocol does not involve the assistance of a directing group or activation of the carbonyl group by any other means. Furthermore, this reaction made use of no toxic CO gas as carbonylating agent; instead, feedstock primary alcohols have been utilized as acylation source. Notably, the synthesis of benzofuranones and indenones is enabled. This strategy was also applied to the synthesis of n-butylphthalide, fenofibrate, pitofenone, and neo-lignan.
- Suchand, Basuli,Sreenivasulu, Chinnabattigalla,Satyanarayana, Gedu
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p. 4832 - 4843
(2019/07/31)
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- Pd(II)-Catalyzed Denitrogenative and Desulfinative Addition of Arylsulfonyl Hydrazides with Nitriles
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A Pd(II)-catalyzed denitrogenative and desulfinative addition of arylsulfonyl hydrazides with nitriles has been successfully achieved under mild conditions. This transformation is a new method for the addition reaction to nitriles with arylsulfonyl hydrazides as arylating agent, thus providing an alternative synthesis of aryl ketones. The reported addition reaction is tolerant to many common functional groups, and works well in the presence of electron-donating and electron-withdrawing substituents. Notably, the reported denitrogenative and desulfinative addition was also appropriate for alkyl nitriles, making this newly developed transformation attractive.
- Meng, Mengting,Yang, Liangfeng,Cheng, Kai,Qi, Chenze
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p. 3275 - 3284
(2018/03/25)
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- Method for preparing aromatic ketone in aqueous phase
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The invention discloses a method for preparing aromatic ketone in an aqueous phase, comprising the following steps: enabling aryl formyl potassium formate and aryl potassium fluoborate to generate decarboxylation acylation reaction in water under the actions of a silver catalyst and an oxidizing agent, and performing treatment after reaction is ended to obtain the disclosed aromatic ketone. According to the preparation method, the silver catalyst replaces a noble metal catalyst, water is taken as a solvent, an aromatic ketone product is obtained with relatively high yield, the adopted catalystis low in cost and easy to obtain, reaction conditions are mild, and meanwhile, the product is good in university, and therefore, the method has good application potential.
- -
-
Paragraph 0046-0049
(2018/04/26)
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- Preparation method of aromatic ketone
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The invention discloses a preparation method of aromatic ketone. Under the effects of a palladium catalyst and a nitrogen-containing ligand, nitrile compounds and arylsulfonylhydrazide take desulfurization addition reaction in an organic solvent; after the reaction is completed, post treatment is performed to obtain aromatic ketone. The reaction is applicable to aromatic nitrile compounds, and isalso applicable to aliphatic nitrile compounds; the reaction realizes the wide substrate applicability and functional group tolerance; the potential application value is realized in the aspect of aryl-carbonyl building.
- -
-
Paragraph 0046; 0047; 0048; 0050
(2018/09/11)
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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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- Method of utilizing continuous flow microreactor to synthesize benzophenone derivative
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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)
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- Pd-Catalyzed Suzuki–Miyaura Cross-Coupling of Arylboronic Acids and α-Iminonitriles through C–CN Bond Activation
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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
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supporting information
p. 4769 - 4775
(2018/09/06)
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- MeZnOMe-mediated reaction of aldehydes with Grignard reagents: A glance into nucleophilic addition/Oppenauer oxidation pathway
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A novel organozincate of RMgX ?MeZnOMe ?LiCl type, formed in situ via transmetalation of Grignard reagent RMgBr ?LiCl with MeZnOMe, is shown to be an excellent organometallic species in the nucleophilic addition/Oppenauer oxidation of aldehydes to generate aromatic ketones in high yield. This transformation allows quick access to structurally diverse aryl, heteroaryl, benzyl and alkyl ketones with broad substrate scope and excellent functional group tolerance.
- Fu, Ying,Ma, Xian-Zhen,Shi, Chun-Zhao,Shen, Tong,Du, Zhengyin
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- Pd-NHC catalysed Carbonylative Suzuki coupling reaction and its application towards the synthesis of biologically active 3-aroylquinolin-4 (1H)-one and acridone scaffolds
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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
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- Highly efficient protocol for the aromatic compounds nitration catalyzed by magnetically recyclable core/shell nanocomposite
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An efficient protocol for the nitration of aromatic compounds in the presence of a catalytic amount of sulfuric acid-functionalized silica-based magnetic core/shell nanocomposite was reported. The designed products were obtained in high yields in relatively short reaction times at room temperature under solvent-free conditions. The nanocatalyst was simply recovered from the reaction mixture by using an external magnet and efficiently reused for several times. The characterization of particle size, morphology and elemental analysis of the nanocatalyst were provided by scanning electron microscopy, transmission electron microscopy and energy-dispersive X-ray spectroscopy analyses, respectively.
- Maleki, Ali,Aghaei, Morteza,Paydar, Reza
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p. 485 - 490
(2017/01/10)
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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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- Ag(i)/persulfate-catalyzed decarboxylative coupling of α-oxocarboxylates with organotrifluoroborates in water under room temperature
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The decarboxylative coupling reaction of α-oxocarboxylates and organotrifluoroborates was carried out smoothly in the presence of catalytic AgNO3 using K2S2O8 as oxidant to generate diarylketone products in high
- Chang, Sheng,Wang, Jian Feng,Dong, Lin Lin,Wang, Dan,Feng, Bo,Shi, Yuan Tai
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p. 51928 - 51934
(2017/11/22)
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- A synthesis of biaryl ketones via the C–S bond cleavage of thiol ester by a Cu/Ag salt
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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
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p. 2751 - 2756
(2017/06/23)
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- Pd/C in Propylene Carbonate: A Sustainable Catalyst–Solvent System for the Carbonylative Suzuki–Miyaura Cross-Coupling Using N-Formylsaccharin as a CO Surrogate
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This work documents the first Pd/C-catalyzed carbonylative Suzuki–Miyaura cross-coupling of aryl iodides with N-formylsaccharin as a CO surrogate. In contrast to previous reaction protocols, which make use of toxic and hazardous solvents, the reaction could be advantageously performed in propylene carbonate as an environmentally benign and sustainable polar aprotic solvent. A range of biaryl ketones, including (4-methoxyphenyl)(3,4,5-trimethoxyphenyl)methanone, an antineoplastic belonging to the phenstatin family, could be synthesized under cocatalyst-free, additive-free and ligand-free conditions. The Pd/C could be recycled up to five times under CO surrogacy with only a marginal decrease in catalytic activity. The reaction could also be scaled up to gram-scale syntheses.
- Gautam, Prashant,Gupta, Rashi,Bhanage, Bhalchandra M.
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p. 3431 - 3437
(2017/07/04)
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- Palladium-Catalyzed suzuki?Miyaura cross-Coupling of amides via site-Selective n?C bond cleavage by cooperative catalysis
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Palladium-catalyzed Suzuki?Miyaura cross-coupling of primary benzamides enabled by a merger of site-selective N,N-di-Boc-activation and cooperative catalysis via N?C bond cleavage for the synthesis of biaryl ketones is reported. We present the synergistic combination of Lewis base and palladium catalysis as a concept to activate inert amide N?C bonds. The mild reaction conditions provide a direct route to structurally diverse ketones. The reaction tolerates a wide range of electrophilic functional groups. Considering the fundamental importance of primary amides as pharmaceutical and synthetic intermediates, the strategy has a potential for developing a diverse array of valuable amide N?C bond functionalization reactions by the synergistic merger of Lewis base and organometallic catalysis.
- Meng, Guangrong,Shi, Shicheng,Szostak, Michal
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p. 7335 - 7339
(2018/05/22)
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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
-
supporting information
p. 4194 - 4197
(2016/09/09)
-
- Magnesium salt promoted tandem nucleophilic addition-Oppenauer oxidation of aldehydes with organozinc reagents
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A magnesium salt promoted synthesis of ketones via tandem nucleophilic addition-Oppenauer oxidation of aldehydes using organozinc chemistry was demonstrated. Magnesium salts concomitantly generated via magnesium metal mediated organohalide zincation exhibit high efficacy for nucleophilic addition of organozinc reagents to aromatic aldehydes and thereafter Oppenauer oxidation whereby ketones are formed in high to excellent yields.
- Fu, Ying,Zhao, Xing Ling,Hügel, Hulmet,Huang, Danfeng,Du, Zhengyin,Wang, Kehu,Hu, Yulai
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supporting information
p. 9720 - 9724
(2016/10/31)
-
- Palladium-Catalyzed Environmentally Benign Acylation
-
Recent trends in research have gained an orientation toward developing efficient strategies using innocuous reagents. The earlier reported transition-metal-catalyzed carbonylations involved either toxic carbon monoxide (CO) gas as carbonylating agent or functional-group-assisted ortho sp2 C-H activation (i.e., ortho acylation) or carbonylation by activation of the carbonyl group (i.e., via the formation of enamines). Contradicting these methods, here we describe an environmentally benign process, [Pd]-catalyzed direct carbonylation starting from simple and commercially available iodo arenes and aldehydes, for the synthesis of a wide variety of ketones. Moreover, this method comprises direct coupling of iodoarenes with aldehydes without activation of the carbonyl and also without directing group assistance. Significantly, the strategy was successfully applied to the synthesis n-butylphthalide and pitofenone.
- Suchand, Basuli,Satyanarayana, Gedu
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p. 6409 - 6423
(2016/08/16)
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- Biaryl Ketones by Suzuki–Miyaura Cross-Coupling of Organotrifluoroborates and Acyl Chlorides
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A procedure for the synthesis of biaryl ketones by a palladium-catalyzed Suzuki–Miyaura cross-coupling reaction between phenyltrifluoroborates and benzoyl chlorides is described. Organotrifluoroborates are unique to other cross-coupling reagents as they have a high functional-group tolerance and are moisture-stable. Moderate to excellent yields were obtained for all substrates tested.
- Forbes, Alaina M.,Meier, G. Patrick,Jones-Mensah, Ebenezer,Magolan, Jakob
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p. 2983 - 2987
(2016/07/11)
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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
-
supporting information
p. 5690 - 5707
(2016/07/06)
-
- KCC-1 supported palladium nanoparticles as an efficient and sustainable nanocatalyst for carbonylative Suzuki-Miyaura cross-coupling
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This work reports a cost-effective and sustainable protocol for the carbonylative Suzuki-Miyaura cross-coupling reaction catalyzed by palladium nanoparticles (Pd NPs) supported on fibrous nanosilica (KCC-1). Under mild reaction conditions, the KCC-1-PEI/Pd catalytic system showed a turnover number (TON) 28-times and a turnover frequency (TOF) 51-times higher than the best supported Pd catalyst reported in the literature for the carbonylative cross-coupling between 4-iodoanisole and phenylboronic acid, as a test reaction. Also, the catalyst could be recycled up to ten times with a marginal loss in activity after the eighth cycle. The high activity of the catalyst can be attributed to the fibrous nature of the KCC-1 support and PEI functionalization provided the enhanced stability.
- Gautam, Prashant,Dhiman, Mahak,Polshettiwar, Vivek,Bhanage, Bhalchandra M.
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supporting information
p. 5890 - 5899
(2016/11/06)
-
- Ruthenium Hydride Complex Supported on Gold Nanoparticle Cored Triazine Dendrimers for C-C Coupling Reactions
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In this work, the unusual ability of a ruthenium hydride catalyst, [RuHCl(PPh3)3CO], supported on gold nanoparticle cored triazine dendrimers in the Suzuki-Miyaura cross-coupling reaction and also in the synthesis of diaryl ketones is reported. [Ru-H@AuNPs-TD] was characterized by Fourier transform infrared spectroscopy, CHNS, TEM, SEM, ICP, and TGA analyses. The ruthenium hydride catalyst was used as a heterogeneous catalyst for the C-C coupling reactions of aryl halides with phenylboronic acids, and the biphenyl derivatives were produced in good to excellent yields. On the other hand, this catalytic system was applied for synthesis of diaryl ketones by the reaction of phenylboronic acids with substituted benzaldehydes. Moreover, this catalyst can be well-dispersed in the reaction medium, conveniently separated from the reaction mixture, and reused several times without significant loss of its activity.
- Daneshvar, Anahita,Moghadam, Majid,Tangestaninejad, Shahram,Mirkhani, Valiollah,Mohammadpoor-Baltork, Iraj,Khalili, Akram
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p. 1747 - 1755
(2016/07/06)
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- Metal-free efficient cross coupling of aromatic aldehydes with aryldiazonium tetrafluoroborates using DTBP as a radical initiator
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A highly efficient, metal-free, one-pot radical route to access diaryl ketones from aromatic aldehydes is reported. The protocol renders cross coupling of aromatic aldehydes with aryl diazonium tetrafluoroborates using inexpensive di-tert-butylperoxide (DTBP) as a radical initiator under mild conditions. The reaction offers a convenient alternative to the Friedel-Crafts acylation for the synthesis of diaryl ketones.
- Tripathi, Shubhangi,Singh, Sachchida N.,Yadav, Lal Dhar S.
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supporting information
p. 4211 - 4214
(2015/06/22)
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- Simple preparation of aryltributylstannanes and its application to one-pot synthesis of diaryl ketones
-
Transfer of aryl group from boron to tin can be achieved by simple treatment of arylboronic acids with tributyltin methoxide at 100 °C for 1 h under neat conditions. The resulting aryltributylstannanes are applicable to one-pot synthesis of diaryl ketones. Thus, Pd-catalyzed cross-coupling reaction with aroyl chlorides is allowed to proceed without isolation step to produce the corresponding diaryl ketones in good to high yields.
- Oikawa, Asuka,Kindaichi, Gan,Shimotori, Yasutaka,Okimoto, Mitsuhiro,Hoshi, Masayuki
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p. 1705 - 1711
(2015/03/30)
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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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- Acyl hydrazides as acyl donors for the synthesis of diaryl and aryl alkyl ketones
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In this communication we describe a novel strategy for the formation of valuable diaryl and aryl alkyl ketones from acyl hydrazides. A wide variety of ketones are prepared and the mild reaction conditions allow for the use of a range of functionalities, especially in the synthesis of diaryl ketones.
- Akhbar, Ahmed R.,Chudasama, Vijay,Fitzmaurice, Richard J.,Powell, Lyn,Caddick, Stephen
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supporting information
p. 743 - 746
(2014/01/06)
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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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- NHC-Pd(II)-Im (NHC=N-heterocyclic carbene, Im=1-methylimidazole) complex catalyzed coupling reaction of arylboronic acids with carboxylic acid anhydrides in water
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A well-defined N-heterocyclic carbene (NHC)-palladium chloride-imidazole complex exhibited high catalytic activity in the coupling reaction of arylboronic acids with carboxylic acid anhydrides in pure water under mild conditions. Under the optimal conditions, all reactions gave the desired coupling products in moderate to high yields.
- Lin, Xiao-Fang,Li, Yao,Li, Shuang-Yan,Xiao, Zheng-Kang,Lu, Jian-Mei
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experimental part
p. 5806 - 5809
(2012/09/08)
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- Mild and efficient nitration of aromatic compounds mediated by transitionmetal complexes
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Aromatic compounds were efficiently nitrated under facile reaction conditions by employing 69% nitric acid catalyzed by transition-metal complexes such as [Co(NH3)5Cl]Cl2, [Cu(NH 3)4]SO4, Mn(acac)3, [Ni(NH 3)6]Cl2, [Ni(en)3]S 2O3, and Hg[Co(SCN)4]. The reaction was completed smoothly at room temperature and afforded corresponding mono-nitro derivatives in quantitative yield. This new method offers efficient and facile regioselective mononitration of aromatic compounds. Taylor & Francis Group, LLC.
- Abdulla,Amina,Kumar, Y. Arun,Arifuddin,Rajanna
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experimental part
p. 2946 - 2951
(2011/09/12)
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- A phosphine-free carbonylative cross-coupling reaction of aryl iodides with arylboronic acids catalyzed by immobilization of palladium in MCM-41
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The phosphine-free heterogeneous carbonylative cross-coupling of aryl iodides with arylboronic acids under an atmospheric pressure of carbon monoxide was achieved in anisole at 80 °C in the presence of a 3-(2-aminoethylamino) propyl-functionalized MCM-41-immobilized palladium(ii) complex [MCM-41-2N-Pd(ii)], yielding a variety of unsymmetrical biaryl ketones in good to high yield. This heterogeneous palladium catalyst exhibited higher activity and selectivity than PdCl2(PPh3)2, can be recovered and recycled by a simple filtration of the reaction solution, and used for at least 10 consecutive trials without any decrease in activity. Our system not only avoids the use of phosphine ligands, but also solves the basic problem of palladium catalyst recovery and reuse.
- Cai, Mingzhong,Peng, Jian,Hao, Wenyan,Ding, Guodong
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experimental part
p. 190 - 196
(2011/03/20)
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- Imidazole-coordinated monodentate NHC-Pd(II) complex derived from proline and its application to the coupling reaction of arylboronic acids with carboxylic acid anhydrides in water at room temperature
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Cleavage of a C-N bond of imidazolium salt derived from N-phenyl-substituted proline was observed in this laboratory. A novel imidazole-coordinated monodentate NHC-Pd(II) complex 5 was obtained as the sole product in good yield in the reaction of imidazolium salt 4 with Pd(OAc) 2 in refluxing THF. The structure of complex 5 was determined unambiguously by an X-ray diffraction. The complex was found to be a good catalyst in the cross-coupling reaction of arylboronic acids with carboxylic acid anhydrides in water at room temperature. Copyright
- Shen, Xiao-Bao,Gao, Ting-Ting,Lu, Jian-Mei,Shao, Li-Xiong
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experimental part
p. 497 - 501
(2012/05/04)
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- Fast and efficient nitration of salicylic acid and some other aromatic compounds over H3PO4/TiO2-ZrO2 using nitric acid
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TiO2-ZrO2 (1/1)-surf with Ti and Zr molar ratio of 1/1 was prepared with surfactant through a sol-gel method. The optimum experimental condition was investigated for nitration of salicylic acid. Then, a number of nitration reactions were carried out with a variety of aromatic compounds in the optimum condition. The 25 wt% H3PO4/TiO2-ZrO2 (1/1)-surf catalyst showed good selectivity and yield in a short time for the nitration of salicylic acid and some other aromatic compounds.
- Kalbasi, Roozbeh Javad,Massah, Ahmad Reza,Zamani, Farzad,Hamid, Javaherian Naghash
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experimental part
p. 397 - 403
(2010/10/20)
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- Efficient and facile method for the nitration of aromatic compounds by nitric acid in micellar media
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Aromatic compounds were efficiently nitrated under mild reaction conditions by employing HNO3 in the presence of anionic (sodium dodecyl sulfate, SDS), cationic (cetyl trimethyl ammonium bromide, CTAB), and nonionic (Triton-X 100) micelles. The reaction rapidly afforded corresponding mononitro derivatives in fair to good yields with high regioselectivity. This new method offers an environmentally safe reaction condition to minimize the waste products.
- Sana,Tasneem,Ali, M. Moazzam,Rajanna,Saiprakash
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experimental part
p. 2949 - 2953
(2009/12/03)
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- An efficient method for aromatic Friedel-Crafts acylation reactions
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Friedel-Crafts acylation of aromatic compounds was carried out using FeCl3-based ionic liquid. This liquid serves as an efficient media as well as a Lewis acid catalyst. The significant advantages of this methodology are excellent yields, short reaction times, mild reaction conditions, environmentally friendly method, simple work-up procedure, low cost, and easy preparation and handling of the catalyst. Copyright
- Khodaei, Mohammad Mehdi,Bahrami, Kiumars,Shahbazi, Fomeida
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p. 844 - 845
(2008/12/22)
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- One-pot synthesis of diaryl ketones from aldehydes via palladium-catalyzed reaction with aryl boronic acids
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A Pd-catalyzed coupling-type reaction of aldehydes and organoboronic acids was achieved in the presence of P(1-nap)3, using Cs2CO3 in toluene, providing diaryl ketones with yields ranged from moderate to excellent. The efficiency of this reaction was demonstrated by the compatibility with nitro, cyano, trifluoromethyl, fluoro and chloro groups. Moreover, the rigorous exclusion of air/moisture is not required in these transformations.
- Qin, Changming,Chen, Jiuxi,Wu, Huayue,Cheng, Jiang,Zhang, Qiang,Zuo, Bing,Su, Weike,Ding, Jinchang
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p. 1884 - 1888
(2008/09/18)
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- Cationic palladium(II)-catalyzed addition of arylboronic acids to nitriles. One-step synthesis of benzofurans from phenoxyacetonitriles
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(Chemical Equation Presented) A cationic palladium complex catalyzed addition of arylboronic acids to nitrites to yield aryl ketones with moderate to good yields was developed. A one-step synthesis of benzofurans from phenoxyacetonitriles under the catalysis of [(bpy)Pd+(μ-OH)] 2(-OTf)2 or [(bpy)Pd2+(H 2O2)2](-OTf)2 was developed which showed that the cationic palladium catalyst is highly active for these addition reactions.
- Zhao, Baowei,Lu, Xiyan
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p. 5987 - 5990
(2007/10/03)
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- Palladium(II)-catalyzed addition of arylboronic acid to nitriles
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The addition of arylboronic acid to nitriles catalyzed by palladium(II) species in the presence of bipyridine as the ligand was developed. The use of bipyridine is crucial for changing the properties of arylpalladium species from more electrophilic to more nucleophilic making the reaction possible.
- Zhao, Baowei,Lu, Xiyan
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p. 6765 - 6768
(2007/10/03)
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- Nitric acid in the presence of P2O5 supported on silica gel - A useful reagent for nitration of aromatic compounds under solvent-free conditions
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A variety of aromatic compounds are nitrated to parent nitro aromatic compounds under solvent-free conditions using 65% nitric acid in the presence of P2O5 supported on silica gel is described. This methodology is useful for nitration of activated and deactivated aromatic rings.
- Hajipour, Abdol Reza,Ruoho, Arnold E.
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p. 8307 - 8310
(2007/10/03)
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- A novel thiourea ligand applied in the Pd-catalyzed Heck, Suzuki and Suzuki carbonylative reactions
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A novel C2 symmetrical and sterically bulky thiourea ligand 1 has been successfully applied to Heck, Suzuki and Suzuki-type carbonylative coupling reactions under aerobic conditions. Since the metal-sulfur bond in the thiourea complexes is stronger than the metal-phosphorus bond of typical phosphine complexes, thiourea ligands generally do not easily dissociate from the metal center under catalytic conditions, which establishes the thiourea 1-based palladium complexes as effective catalysts for the palladium-catalyzed cross-coupling reactions.
- Mingji, Dai,Liang, Bo,Wang, Cuihua,You, Zejin,Xiang, Jing,Dong, Guangbin,Chen, Jiahua,Yang, Zhen
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p. 1669 - 1673
(2007/10/03)
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- Palladium-catalyzed reactions of arylboron compounds with carboxylic acid chlorides
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Reactions of sodium tetraarylborates and arylboronic acids with acyl chlorides in the presence of palladium salts afford non-symmetrical ketones in high yields under mild conditions.
- Korolev,Bumagin
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p. 364 - 369
(2007/10/03)
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- Pd-catalyzed carbonylative cross-coupling reactions by triorganoindiums: Highly efficient transfer of organic groups attached to indium under atmospheric pressure
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(Matrix presented) A highly atom-efficient synthetic method of unsymmetrical ketones was developed by using trialkyl- and triarylindiums, which could be employed as effective cross-coupling partners in Pd-catalyzed carbonylative cross-coupling reactions with a variety of organic electrophiles. The present method produced unsymmetrical ketones and 1,4-diacylbenzenes in good yields with highly efficient transfer of almost all the organic groups attached to the indium under atmospheric pressure of CO gas in THF at 66°C.
- Lee, Phil Ho,Lee, Sung Wook,Lee, Kooyeon
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p. 1103 - 1106
(2007/10/03)
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