- Low pressure Pd-catalyzed carbonylation in an ionic liquid using a multiphase microflow system
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A low pressure microflow system was developed for palladium-catalyzed multiphase carbonylation reactions in an ionic liquid. The microflow system resulted in superior selectivity and higher yields in carbonylative Sonogashira coupling and amidation reactions of aryl iodides compared to the conventional batch system. The Royal Society of Chemistry 2006.
- Rahman, Md. Taifur,Fukuyama, Takahide,Kamata, Naoya,Sato, Masaaki,Ryu, Ilhyong
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- Pd-Catalyst Containing a Hemilabile P,C-Hybrid Ligand in Amino Dicarbonylation of Aryl Halides for Synthesis of α-Ketoamides
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The amino dicarbonylation of aryl halides affording α-ketoamides with Pd catalysts is highly dependent on the stereoelectronic properties of the involved ligands. Ionic diphosphine ligand L4 can serve as precursor of a hemilabile P,C (phosphine, carbene)-hybrid ligand to form a stable Pd(II)-complex, Pd-L4. In contrast, analogues L1-L3 with a similar 1-(thiophen-3-yl)-benzimidazolyl skeleton behave as typical (mono/di)phosphines. The catalytic system resulting from the complexation of PdCl2(MeCN)2 and L4 exhibits good catalytic performance in terms of aryl iodides conversion (81-95%) and α-ketoamide selectivity (80-91%), as well as the available recyclability in the RTIL of [Bpy]BF4. The in situ FT-IR analysis reveals that the PdCl2(MeCN)2-L4 catalytic system favors the amino dicarbonylation toward α-ketoamides according to the proposed mechanism of cycle I, which involves two independent CO-insertion steps.
- Yang, Shu-Qing,Yao, Yin-Qing,Chen, Xiao-Chao,Lu, Yong,Zhao, Xiao-Li,Liu, Ye
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p. 1032 - 1041
(2021/05/07)
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- Visible-light-mediated direct access to α-ketoamides by dealkylative amidation of tertiary amines with benzoylformic acids
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A visible-light induced direct amidation of benzoylformic acids with tertiary amines has been explored. Tertiary amines underwent N-dealkylative amidation with α-keto acid in the presence of [Ir{dFCF3ppy}2(bpy)]PF6 and Cs
- Zhang, Zhiguo,Liu, Fangnan,Chen, Jingwen,Zhou, Kai,Bao, Zongbi,Su, Baogen,Yang, Qiwei,Ren, Qilong,Yang, Yiwen
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supporting information
(2019/10/02)
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- Water dispersed gold nanoparticles catalyzed aerobic oxidative cross-dehydrogenative coupling: An efficient synthesis of α-ketoamides in water
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An effective green synthesis of α-ketoamides was developed for the first time in water via gold nanoparticles (AuNPs) catalyzed aerobic oxidative cross-dehydrogenative coupling of secondary amines with phenylglyoxals with a broad substrate scope.
- Thirukovela, Narasimha Swamy,Balaboina, Ramesh,Vadde, Ravinder,Sekhar Vasam, Chandra
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supporting information
p. 3749 - 3752
(2018/09/17)
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- Versatile Heterogeneous Palladium Catalysts for Diverse Carbonylation Reactions under Atmospheric Carbon Monoxide Pressure
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Herein, we report a versatile carbonylation protocol using heterogeneous Pd0 nanoparticles supported on the metal–organic frameworks (MOFs) MIL-88B-NH2 (Fe/Cr). The synthesis of a vast array of carbonyls, which includes amides, esters, carboxylic acids, and α-ketoamides, was achieved through mono- and dicarbonylation reactions. The selectivity could be controlled simply by tuning the reaction conditions. Superior activity and selectivity were recorded in some cases compared to that achieved with commercial Pd/C. However, the utility of an elaborate catalyst support is questionable and important reactivity and recyclability issues are discussed.
- Vico Solano, Marta,González Miera, Greco,Pascanu, Vlad,Inge, A. Ken,Martín-Matute, Belén
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p. 1089 - 1095
(2018/02/06)
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- nBu4NI-Mediated oxidation of methyl ketones to α-ketoamides: using ammonium, primary and secondary amine-salt as an amine moiety
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Presented here is the first example of synthesizing an array of primary-, secondary-, and tertiary-α-ketoamides with a non-metal catalyst nBu4NI from methyl ketones and inexpensive readily available amine/ammonium salts; the reactions proceeded smoothly under mild conditions, TBHP was used as an oxidant and the corresponding α-ketoamides were afforded in moderate to excellent yields.
- Wang, Dan,Zhang, Kuan,Jia, Luhan,Zhang, Danting,Zhang, Yue,Cheng, Yujia,Lin, Chang,Wang, Bo
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p. 3427 - 3434
(2017/04/24)
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- Transition metal-free synthesis of α-ketoamides from arylmethyl ketones and alkylphosphoramides
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A transition metal-free protocol has been developed for the synthesis of α-ketoamides from aryl methyl ketones and alkylphosphoramides in the presence of oxidant, aqueous tert-butyl hydroperoxide (TBHP). A series of aryl methyl ketones having both electron-donating as well as electron-withdrawing groups were successfully employed for the synthesis of their corresponding α-ketoamides using hexamethylphosphoramide and other alkylphosphoramides.
- Behera, Ahalya,Ali, Wajid,Tripathy, Manisha,Sahoo, Diptimayee,Patel, Bhisma K.
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p. 91308 - 91313
(2016/10/09)
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- Room temperature copper-catalyzed oxidative amidation of terminal alkynes for the synthesis of α-ketoamides using: O -benzoyl hydroxylamines as aminating reagent and oxidant
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A novel and convenient copper-catalyzed oxidative amidation for the synthesis of α-ketoamides has been successfully developed, which uses easily available O-benzoyl hydroxylamines as aminating reagent and oxidant. The reaction proceeds smoothly at room temperature and is compatible with a range of substrates to give the desired products in moderate to good yields.
- Shen, Guodong,Zhao, Lingyu,Wang, Yichen,Zhang, Tongxin
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p. 78307 - 78310
(2016/09/09)
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- Cu(i)-Functionalized SBA-16: An efficient catalyst for the synthesis of α-ketoamides under moderate conditions
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An efficient catalyst based on the cage-like mesoporous material SBA-16 as the support and Cu(i) as active sites has been successfully prepared. The catalyst demonstrated high catalytic activity (up to 88%) in the direct oxidative synthesis of α-ketoamides between acetophenone and piperidine, employing O2 from open air as the oxidant without other additives. A heterogeneous catalyst was applied in this reaction for the first time, and the catalyst could be easily separated from the reaction system by filtration and reused several times without a significant loss of activity.
- Zhang, Xueyao,Yang, Honglei,Huo, Yong,Li, Jing,Ma, Jianxin,Ma, Jiantai
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p. 8972 - 8983
(2016/06/09)
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- Synthesis of α -Ketoamides by Copper-Catalyzed Reactions of Phenylacetic Acids with N,N -Dialkylformamides
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A new synthetic approach for α-ketoamides was achieved by copper-catalyzed coupling reactions between N,N-dialkylformamides and phenylacetic acids. A variety of substrates were well tolerated to give yields of 46-87% (17 examples). A 13C-labeli
- Zhang, Lanping,Pu, Junnan,Ren, Jiayu,Li, Zhengkai,Xiang, Haifeng,Zhou, Xiangge
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p. 1848 - 1856
(2015/08/03)
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- Metal-free tandem oxidative aryl migration and C-C bond cleavage: Synthesis of α-ketoamides and esters from acrylic derivatives
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A novel tandem metal-free oxidative aryl migration/C-C bond-cleavage reaction, mediated by hypervalent iodine reagent, has been discovered. The presented transformation provided straightforward access to important α-ketoamide and α-ketoester derivatives from readily available acrylic derivatives via a concerted process of 1,2-aryl shift concomitant with C-C bond cleavage.
- Liu, Le,Du, Liang,Zhang-Negrerie, Daisy,Du, Yunfei,Zhao, Kang
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supporting information
p. 5772 - 5775
(2015/02/19)
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- Aryl-palladium-NHC complex: Efficient phosphine-free catalyst precursors for the carbonylation of aryl iodides with amines or alkynes
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A series of aryl-palladium-NHC compounds was prepared according to the reported methods and their catalytic activity in the carbonylation of aryl iodides to synthesize α-keto amides and alkynones was examined. These practical aryl-palladium-NHC complexes have shown highly efficient catalyzed carbonylation and Sonogashira carbonylation reactions, with high turnover number in synthesis of α-keto amides (TON = 4300) and in synthesis of alkynones (TON = 980).
- Zhang, Chunyan,Liu, Jianhua,Xia, Chungu
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supporting information
p. 9702 - 9706
(2015/02/19)
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- Phosphine-free, efficient double carbonylation of aryl iodides with amines catalyzed by water-insoluble and water-soluble N-heterocyclic carbene-amine palladium complexes
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The water-insoluble and water-soluble N-heterocyclic carbene (NHC)-amine palladium complexes, Ipr-Pd(deba)Cl and SO3-Ipr-Pd(deba)Cl, were synthesized. Both catalysts exhibit excellent activity in the phosphine-free double carbonylation of aryl iodides with amines to produce α-keto amides. Moreover, as the water-soluble catalyst exhibits significant compatibility in the aqueous phase with the activities of different Pd-NHC complexes, we conclude that the intramolecular amine ligand strongly affects the selectivity of the products in double carbonylation reaction and serves as an alternative of phosphine ligands.
- Wang, Yan,Yang, Xiaolong,Zhang, Chunyan,Yu, Jianqiang,Liu, Jianhua,Xia, Chungu
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p. 2539 - 2546
(2014/09/29)
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- Silver-catalyzed amidation of benzoylformic acids with tertiary amines via selective carbon-nitrogen bond cleavage
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A novel approach towards the synthesis of α-ketoamides using tertiary amines as nitrogen group sources via C-N bond cleavage has been developed. In the presence of Ag2CO3 and K2S 2O8, α-keto acids reacted with tertiary amines to afford the corresponding α-ketoamides in good yields. The Royal Society of Chemistry 2013.
- Zhang, Xiaobin,Yang, Wenchao,Wang, Lei
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p. 3649 - 3654
(2013/06/26)
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- Double carbonylation of aryl iodides with diethylamine catalyzed by dinuclear palladium complexes
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Dinuclear palladium complexes bridged by a novel PNNP ligand, N,N ′-bis[(2-diphenylphosphino)phenylformamidinate (dpfam), were found to be very efficient and selective catalysts for the double carbonylation of iodobenzene with diethylamine using K3PO4 as base and 1,4-dioxane as solvent with a TON up to 105 and selectivity of 96%.
- Tsukada, Naofumi,Ohba, Yoichi,Inoue, Yoshio
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p. 436 - 443
(2007/10/03)
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- Hypervalent iodine in synthesis 68: Palladium-catalysed double carbonylation of diaryliodonium salts to give α-keto-amides
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In the presence of a palladium catalyst and the cocatalyst Cul, several diaryliodonium salts have been converted into α-keto amides on treatment with secondary amines and carbon monoxide in good yield and selectivity under mild reaction conditions.
- Zhou, Tao,Chen, Zhen-Chu
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p. 116 - 117
(2007/10/03)
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- Reactivity of the α-ketoacyl ligand in Cp′(L)(NO)Mn-C{O}C{O}tol with electrophiles, nucleophiles, and alkynes
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The reactivity of the α-ketoacyl complexes Cp′(L)(NO)Mn-C{O}C{O}Tol (Cp′ = C5H4Me; 1, L = CO; 2, L = PPh3) with a variety of electrophiles, nucleophiles, and alkynes has been explored. Complex 2 undergoes protonation at the α-carbonyl oxygen at low temperature to produce a hydroxy-carbene complex. This species rearranges upon warmup by breaking the carbon-carbon bond of the α-ketoacyl ligand to give 4-methylbenzaldehyde and [Cp′Mn(PPh3)(NO)(CO)]+ (6). Oxidation of complex 2 with either [Cp2Fe]+ or Ag+ also results in the formation of complex 6 along with a mixture of organic products in which TolC{O}C{O}Tol dominates. These products indicate that oxidation induces cleavage of the α-ketoacyl carbon-carban bond to form 6 and TolC{O}. radicals. Complex 1 reacts with NEt2H under photochemical conditions to give the α-ketoamide TolC{O}C{O}NEt2. Upon photolysis, complex 1 reacts with alkynes RC≡CR′ to form metallacycles of the type Cp(CO)(NO)Mn=CR-CR′=C(C{O}Tol)O that result from coupling of the alkyne and the α-ketoacyl ligand. The metallacycles can be demetalated by treatment with HCl to give vinyl α-diones that are the net result of cis addition of the α-ketoacyl ligand and a proton across the alkyne triple bond.
- Bassner, Sherri L.,Sheridan, John B.,Kelley, Colleen,Geoffroy, Gregory L.
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p. 2121 - 2126
(2008/10/08)
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- Palladium-Catalysed Double Carbonylation of Aryl Halides To Give α-Keto Amides. Mechanistic Studies
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Various aryl halides are catalytically converted into α-keto amides and amides on treatment with secondary amines and carbon monoxide.Palladium complexes containing tertiary phosphine ligands, particularly diphenylmethylphosphine and 1,4-bis(diphenylphosphino)butane, are most effective among other transition-metal complexes.Detailed examination of factors controlling the reaction rates and selectivity for α-keto amide formation revealed the following characteristics of the reactions. (a) Reactivity of phenyl halide decreases in the order PhI > PhBr >> PhCl. (b) Oxidative addition of phenyl bromide constitutes the rate-determining step in double carbonylation of phenyl bromide, whereas in the reaction of phenyl iodide the rate determinig step is associated with the reaction of a catalitically active palladium species with carbon monoxide. (c) Introduction of an electron-withdrawing substituent into the para position of phenyl halide enhances the reactivity but decreases the selectivity for α-keto amide. (d) Employment of amines of high basicity (pKb Et2NH > piperidine > hexamethyleneimine > Me2NH > pyrrolidine probably reflects the decrease in steric bulkiness of amines. (f) Although primary amines are in general not suitable for the double carbonylation, tert-butylamine can be used because of its inertness to the product α-keto amide.Reactivity of trans-PdPh(I)(PMePh2)2 and trans-Pd(COPh)I(PMePh2)2, supposed intermediates in the catalytic reaction of PhI, toward amines and CO was examined.The relative reactivity of six secondary amines with the benzoylpalladium complex increasing in the order Pr2NH Et2NH piperidine Me2NH hexamethyleneimine pyrrolidine was found to be inversely correlated with decreasing selectivity order for α-keto amide formation in the catalytic systems.On the basis of the experimental results, a mechanism consisting of two catalytic cycles to produce α-keto amides and amides has been proposed.
- Ozawa, Fumiyuki,Soyama, Hidehiko,Yanagihara, Hisayoshi,Aoyama, Issei,Takino, Hiroaki,et al.
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p. 3235 - 3245
(2007/10/02)
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- CATALYTIC DOUBLE CARBONYLATION OF ORGANOHALOGEN COMPOUNDS PROMOTED BY PALLADIUM COMPLEXES
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Various organohalogen compounds can be catalytically converted into α-keto amides on reaction with carbon monoxide and amines.Tertiary phosphine-coordinated palladium compounds are particularly suitable as the double carbonylation catalyst.
- Ozawa, Fumiyuki,Soyama, Hidehiko,Yamamoto, Takakazu,Yamamoto, Akio
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p. 3383 - 3386
(2007/10/02)
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