- Complementary Photocatalytic Toolbox: Control of Intramolecular endo-versus exo-trig Cyclizations of α-Phenyl Olefins to Oxaheterocyclic Products
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The regioselectivity of the intramolecular cyclization of bifunctional α-phenyl alkenes can be controlled simply by the choice of the organic chromophore as the photocatalyst. The central photoredox catalytic reaction in both cases is a nucleophilic addition of the hydroxyl function to the olefin function of the substrates. N,N-(4-Diisobutylaminophenyl) phenothiazine catalyzes exo-trig cyclizations, whereas 1,7-dicyanoperylene-3,4,9,10-tetracarboxylic acid bisimides catalyze endo-trig additions to products with anti-Markovnikov regioselectivity. We preliminarily report the photoredox catalytic conversions of 11 representative substrates into 20 oxaheterocycles in order to demonstrate the similarity, but also the complementarity, of these two variants in this photoredox catalytic toolbox.
- Belov, Arina,Steuernagel, Desirée,Wagenknecht, Hans-Achim,Weick, Fabian
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- Nickel-Catalyzed Selective Synthesis of α-Alkylated Ketones via Dehydrogenative Cross-Coupling of Primary and Secondary Alcohols
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Herein, we describe an isolable, air-stable, homogeneous, nickel catalyst that performs dehydrogenative cross-coupling reaction between secondary and primary alcohols to result α-alkylated ketone products selectively. The sequence of steps involve in this one-pot reaction is dehydrogenation of both alcohols, condensation between the ketone and the aldehyde, and hydrogenation of the in situ-generated α,β-unsaturated ketone. Preliminary mechanistic investigation hints a radical mechanism following borrowing hydrogen reaction. (Figure presented.).
- Bains, Amreen K,Biswas, Ayanangshu,Adhikari, Debashis
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supporting information
p. 47 - 52
(2021/10/14)
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- BTP-Rh@g-C3N4 as an efficient recyclable catalyst for dehydrogenation and borrowing hydrogen reactions
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Highly active catalysts play an important role in modern catalysis. A novel and efficient ligand benzotriazole-pyrimidine (BTP) and the corresponding rhodium composite on C3N4 were successfully synthesized. The resulting rhodium composite was fully characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), x-ray diffraction (XRD), thermogravimetric analysis (TGA), and x-ray photoelectron spectroscopy (XPS). The obtained composite exhibited good catalytic activity and good recovery performance in the synthesis of quinoxaline from 2-aminobenzyl alcohol and benzonitrile, and more than 20 quinoxalines were obtained in good yields. Additionally, it also showed that rhodium composite could achieved good catalytic performance in the synthesis of functionalized ketone through borrowing hydrogen strategy.
- Luo, Lan,Liu, Hongqiang,Zeng, Wei,Hu, Wenkang,Wang, Dawei
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- Synthesis of α-Alkylated Ketones via Selective Epoxide Opening/Alkylation Reactions with Primary Alcohols
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A new method for converting terminal epoxides and primary alcohols into α-alkylated ketones under borrowing hydrogen conditions is reported. The procedure involves a one-pot epoxide ring opening and alkylation via primary alcohols in the presence of an N-heterocyclic carbene iridium(I) catalyst, under aerobic conditions, with water as the side product.
- Gen?, Serta?,Gülcemal, Süleyman,Günnaz, Salih,?etinkaya, Bekir,Gülcemal, Derya
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supporting information
p. 5229 - 5234
(2021/07/19)
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- Iridium Complexes as Efficient Catalysts for Construction of α-Substituted Ketones via Hydrogen Borrowing of Alcohols in Water
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Ketones are of great importance in synthesis, biology, and pharmaceuticals. This paper reports an iridium complexes-catalyzed cross-coupling of alcohols via hydrogen borrowing, affording a series of α-alkylated ketones in high yield (86 %–95 %) and chemoselectivities (>99 : 1). This methodology has the advantages of low catalyst loading (0.1 mol%) and environmentally benign water as the solvent. Studies have shown the amount of base has a great impact on chemoselectivities. Meanwhile, deuteration experiments show water plays an important role in accelerating the reduction of the unsaturated ketones intermediates. Remarkably, a gram-scale experiment demonstrates this methodology of iridium-catalyzed cross-coupling of alcohols has potential application in the practical synthesis of α-alkylated ketones.
- Luo, Nianhua,Zhong, Yuhong,Wen, Huiling,Shui, Hongling,Luo, Renshi
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p. 1355 - 1364
(2021/03/03)
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- Ir(NHC)-Catalyzed Synthesis of β-Alkylated Alcohols via Borrowing Hydrogen Strategy: Influence of Bimetallic Structure
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Multi N-heterocyclic carbene(NHC)-modified iridium catalysts were employed in the β-alkylation of alcohols; dimerization of primary alcohols (Guerbet reaction), cross-coupling of secondary and primary alcohols, and intramolecular cyclization of alcohols. Mechanistic studies of Guerbet reaction, including kinetic experiments, mass analysis, and density functional theory (DFT) calculation, were employed to explain the fast reaction promoted by bimetallic catalysts, and the dramatic reactivity increase of monometallic catalysts at the late stage of the reaction. (Figure presented.).
- Sung, Kihyuk,Lee, Mi-hyun,Cheong, Yeon-Joo,Kim, Yu Kwon,Yu, Sungju,Jang, Hye-Young
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supporting information
p. 3090 - 3097
(2021/05/10)
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- Unveiling the catalytic nature of palladium-N-heterocyclic carbene catalysts in the α-alkylation of ketones with primary alcohols
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We report herein the synthesis of four new Pd-PEPPSI complexes with backbone-modified N-heterocyclic carbene (NHC) ligands and their application as catalysts in the α-alkylation of ketones with primary alcohols using a borrowing hydrogen process and tandem Suzuki-Miyaura coupling/α-alkylation reactions. Among the synthesized Pd-PEPPSI complexes, complex2chaving 4-methoxyphenyl groups at the 4,5-positions and 4-methoxybenzyl substituents on the N-atoms of imidazole exhibited the highest catalytic activity in the α-alkylation of ketones with primary alcohols (18 examples) with yields reaching up to 95%. Additionally, complex2cwas demonstrated to be an effective catalyst for the tandem Suzuki-Miyaura-coupling/α-alkylation of ketones to give biaryl ketones with high yields. The heterogeneous nature of the present catalytic system was verified by mercury poisoning and hot filtration experiments. Moreover, the formation of NHC-stabilized Pd(0) nanoparticles during the α-alkylation reactions was identified by advanced analytical techniques.
- ?etinkaya, Bekir,Ero?lu, Zafer,Gülcemal, Süleyman,Metin, ?nder,Ovezova, Mamajan
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supporting information
p. 10896 - 10908
(2021/08/17)
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- C-C coupling formation using nitron complexes
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A series of RuII (1), RhIII (2), IrIII (3, 4), IrI (5) and PdII (6-9) complexes of the 'instant carbene' nitron were prepared and characterized by 1H- and 13C-NMR, FT-IR and elemental analysis. The molecular structures of complexes 1-4 and 6 were determined by X-ray diffraction studies. The catalytic activity of the complexes (1-9) was evaluated in alpha(α)-alkylation reactions of ketones with alcohol via the borrowing hydrogen strategy under mild conditions. These complexes were able to perform this catalytic transformation in a short time with low catalyst and base amounts under an air atmosphere. Also, the PdII-nitron complexes (6-9) were applied in the Suzuki-Miyaura C-C coupling reaction and these complexes successfully initiated this reaction in a short time (30 minutes) using the H2O/2-propanol (1.5?:?0.5) solvent system. The DFT calculations revealed that the Pd0/II/0 pathway was more preferable for the mechanism
- Sevim, Mehmet,Kavukcu, Serdar Batikan,Kinal, Arma?an,?ahin, Onur,Türkmen, Hayati
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supporting information
p. 16903 - 16915
(2020/12/18)
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- Synthesis and catalytic applications of Ru and Ir complexes containing N,O-chelating ligand
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A series of monometallic complexes (Ru1–3, Ir1–3) which have N,O-chelating ligand (pyrazine-2-carboxylate (1), pyridine-2-carboxylate (2), quinoline carboxylate(3) and bimetallic complexes (Ru4,5, Ir4,5) bridged by pyrazine-2,3- dicarboxylate (4) and imidazole-4,5-dicarboxylate(5) were synthesized and characterized by 1H-, 13C NMR, FT-IR, and elemental analysis. The crystal structure of Ir2 was determined by X-ray crystallography. The complexes (Ru1–5, Ir1–5) were applied to investigate the electronic and steric effect of ligand in their catalytic activities in transfer hydrogenation and alpha(α)-alkylation reaction of ketones with alcohols. The activities of iridium complexes (Ir1–5) were much more efficient than ruthenium complexes (Ru1–5). The highest activity for both reactions was observed for the complex (Ir2) with pyridine-2-carboxylate. The Ir hydride species was monitored for both reactions.
- Pakyapan, Bilge,Kavukcu, Serdar Bat?kan,?ahin, Zarife Sibel,Türkmen, Hayati
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- Proton-Coupled Electron Transfer: Transition-Metal-Free Selective Reduction of Chalcones and Alkynes Using Xanthate/Formic Acid
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Highly chemoselective reduction of α,β-unsaturated ketones to saturated ketones and stereoselective reduction of alkynes to (E)-alkenes has been developed under a transition-metal-free condition using a xanthate/formic acid mixture through proton-coupled electron transfer (PCET). Mechanistic experiments and DFT calculations support the possibility of a concerted proton electron-transfer (CPET) pathway. This Birch-type reduction demonstrates that a small nucleophilic organic molecule can be used as a single electron-transfer (SET) reducing agent with a proper proton source.
- Prasanna, Ramanathan,Guha, Somraj,Sekar, Govindasamy
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supporting information
p. 2650 - 2653
(2019/04/17)
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- One-Pot Synthesis of O-Heterocycles or Aryl Ketones Using an InCl3/Et3SiH System by Switching the Solvent
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An efficient one-pot synthesis of O-heterocycles or aryl ketones has been achieved using Et3SiH in the presence of InCl3 via a sequential ionic hydrogenation reaction by switching the solvent. This methodology can be used to construct C-O bonds and to prepare conjugate reduction products, including chromans, tetrahydrofurans, tetrahydropyrans, dihydroisobenzofurans, dihydrochalcones, and 1,4-diones in a facile manner. In addition, a novel plausible mechanism involving a conjugate reduction and a tandem reductive cyclization was verified by experimental investigations.
- Jia, Wenqiang,Xi, Qiumu,Liu, Tianqi,Yang, Minjian,Chen, Yonghui,Yin, Dali,Wang, Xiaojian
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p. 5141 - 5149
(2019/05/10)
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- Piano-stool Ru (II) arene complexes that contain ethylenediamine and application in alpha-alkylation reaction of ketones with alcohols
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A series of piano-stool Ru (II) complexes (Ru1–7) bearing ethylenediamine with aryl and aliphatic groups were prepared and fully characterized by 1H, 13C, 19F and 31P NMR spectroscopy, FT-IR and elemental analysis. The crystal structures of Ru2–4 and Ru7 were determined by X-ray crystallography. They were successfully applied to the alpha(α)-alkylation of aliphatic and aromatic ketones with alcohols via the borrowing hydrogen strategy in mild reaction conditions within a short time. The catalytic system has a broad substrate scope, which allows the synthesis of alpha alkylated ketones with excellent yields. The electronic and steric effects of complexes on catalytic activity were analysed. The influence of the carbon chain length of the ligand on the alpha-alkylation reaction of ketones was also investigated. The catalytic cycle was also examined by 1H-NMR spectroscopy in d8-toluene.
- Kavukcu, Serdar Bat?kan,Günnaz, Salih,?ahin, Onur,Türkmen, Hayati
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- Reaction condition controlled nickel(ii)-catalyzed C-C cross-coupling of alcohols
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The challenge in the C-C cross-coupling of secondary and primary alcohols using acceptorless dehydrogenation coupling (ADC) is the difficulty in accurately controlling product selectivities. Herein, we report a controlled approach to a diverse range of β-alkylated secondary alcohols, α-alkylated ketones and α,β-unsaturated ketones using the ADC methodology employing a Ni(ii) 4,6-dimethylpyrimidine-2-thiolate cluster catalyst under different reaction conditions. This catalyst could tolerate a wide range of substrates and exhibited a high activity for the annulation reaction of secondary alcohols with 2-aminobenzyl alcohols to yield quinolines. This work is an example of precise chemoselectivity control by careful choice of reaction conditions.
- Zhang, Meng-Juan,Li, Hong-Xi,Young, David J.,Li, Hai-Yan,Lang, Jian-Ping
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supporting information
p. 3567 - 3574
(2019/04/14)
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- Synthesis and Structures of Arene Ruthenium (II)–NHC Complexes: Efficient Catalytic α-alkylation of ketones via Hydrogen Auto Transfer Reaction
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A panel of six new arene Ru (II)-NHC complexes 2a-f, (NHC?=?1,3-diethyl-(5,6-dimethyl)benzimidazolin-2-ylidene 1a, 1,3-dicyclohexylmethyl-(5,6-dimethyl)benzimidazolin-2-ylidene 1b and 1,3-dibenzyl-(5,6-dimethyl)benzimidazolin-2-ylidene 1c) were synthesized from the transmetallation reaction of Ag-NHC with [(η6-arene)RuCl2]2 and characterized. The ruthenium (II)-NHC complexes 2a-f were developed as effective catalysts for α-alkylation of ketones and synthesis of bioactive quinoline using primary/amino alcohols as coupling partners respectively. The reactions were performed with 0.5?mol% catalyst load in 8?h under aerobic condition and the maximum yield was up to 96%. Besides, the different alkyl wingtips on NHC and arene moieties were studied to differentiate the catalytic robustness of the complexes in the transformations.
- Balamurugan, Gunasekaran,Balaji, Sundarraman,Ramesh, Rengan,Bhuvanesh, Nattamai S.P.
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- Dirhodium(ii)/P(t-Bu)3 catalyzed tandem reaction of α,β-unsaturated aldehydes with arylboronic acids
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Phosphine ligated dirhodium(ii) acetate is advocated as a catalyst for the synthesis of aryl alkyl ketones by the tandem reaction of α,β-unsaturated aromatic or aliphatic aldehydes with arylboronic acids. This tandem procedure included arylation followed by the isomerization reaction. This method exhibits good functional group tolerance and has a broad substrate scope. With the conjugated aldehydes, the one-step synthesis of γ,δ-unsaturated ketones was realized through this reaction. It is noteworthy that the length of the Rh-P bond is an important factor affecting catalytic reactions. The comparative analysis of the crystal structures of axially alkylphosphane and arylphosphane ligated dirhodium(ii) acetate revealed that the shorter Rh-P bond length favors the isomerization process as compared to the longer one. In addition, the dirhodium(ii) compound can be recovered after the completion of the reaction.
- Ma, Ziling,Wang, Yuanhua
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supporting information
p. 7470 - 7476
(2018/10/24)
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- Iridium(I)-Catalyzed Alkylation Reactions to Form α-Alkylated Ketones
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A highly effective and green procedure for the formation of α-alkylated ketones has been disclosed via the reaction of primary alcohols with secondary alcohols and ketones by using [IrCl(COD)(NHC)] complexes as a catalyst. Various α-alkylated ketones were obtained in high yields from the alkylation of alcohol with alcohol and ketone with alcohol through a borrowing hydrogen reaction by using 0.05-0.5 mol % iridium(I) and a catalytic amount of KOH (5-10 mol %) as the base under air atmosphere and within very short reaction times.
- Gen?, Serta?,Günnaz, Salih,?etinkaya, Bekir,Gülcemal, Süleyman,Gülcemal, Derya
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p. 2875 - 2881
(2018/03/09)
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- NNN pincer Ru(II)-complex-catalyzed α-alkylation of ketones with alcohols
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A series of novel ruthenium(II) complexes supported by a symmetrical NNN ligand were prepared and fully characterized. These complexes exhibited good performance in transfer hydrogenation to form new C-C bonds using alcohols as the alkylating agents, generating water as the only byproduct. A broad range of substrates, including (hetero)aryl- or alkyl-ketones and alcohols, were well tolerated under the optimized conditions. Notably, α-substituted methylene ketones were also investigated, which afforded α-branched steric hindrance products. A potential application of α-alkylation of methylene acetone to synthesize donepezil was demonstrated, which provided the desired product in 83% yield. Finally, this catalytic system could be applied to a one-pot double alkylation procedure with sequential addition of two different alcohols. The current protocol is featured with several characteristics, including a broad substrate scope, low catalyst (0.50 mol %) loadings, and environmental benignity.
- Cao, Xiao-Niu,Wan, Xiao-Min,Yang, Fa-Liu,Li, Ke,Hao, Xin-Qi,Shao, Tian,Zhu, Xinju,Song, Mao-Ping
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p. 3657 - 3668
(2018/04/14)
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- Manganese-Catalyzed α-Alkylation of Ketones, Esters, and Amides Using Alcohols
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Herein we report the manganese-catalyzed C-C bond-forming reactions via α-alkylation of ketones, amides, and esters, using primary alcohols. β-Alkylation of secondary alcohols by primary alcohols to obtain α-alkylated ketones is also reported. The reactions are catalyzed by a (iPr-PNP)Mn(H)(CO)2 pincer complex under mild conditions in the presence of (catalytic) base liberating water (and H2 in the case of secondary alcohol alkylation) as the sole byproduct.
- Chakraborty, Subrata,Daw, Prosenjit,Ben David, Yehoshoa,Milstein, David
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p. 10300 - 10305
(2018/10/20)
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- Cobalt-Catalyzed α-Alkylation of Ketones with Primary Alcohols
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An ionic cobalt-PNP complex is developed for the efficient α-alkylation of ketones with primary alcohols for the first time. A broad range of ketone and alcohol substrates were employed, leading to the isolation of alkylated ketones with yields up to 98%. The method was successfully applied to the greener synthesis of quinoline derivatives while using 2-aminobenzyl alcohol as an alkylating reagent.
- Zhang, Guoqi,Wu, Jing,Zeng, Haisu,Zhang, Shu,Yin, Zhiwei,Zheng, Shengping
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supporting information
p. 1080 - 1083
(2017/03/14)
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- Efficient alkylation of ketones with primary alcohols catalyzed by ruthenium(II)/P,N ligand complexes
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An efficient catalytic system containing [RuCl2(η6-p-cymene)]2 and one P,N ligand, N-diphenylphosphino-2-aminopyridine (L1) was loaded in catalyzing the alkylation of ketones with primary alcohols for a diverse array of substrates. Other five P,N ligands based on pyridin-2-amine and pyrimidin-2-amine were also examined in this reaction to explore the influence of steric hindrance and electronic effects. Monitoring by 1H NMR and ESI-MS reveals a stable cationic L1-coordinated ruthenium hydride intermediate, identified as [Ru(η6-p-cymene)(κ2-L1)H]+. Organic intermediates consistent with a three-step dehydrogenation, alkylation and hydrogenation pathway were also observed. The final step in this reaction, the ruthenium-catalysed transfer hydrogenation reduction of α,β-unsaturated ketone with benzyl alcohol was performed separately.
- Liu, Shi-Yuan,Xu, Lin-Yan,Liu, Chun-Yu,Ren, Zhi-Gang,Young, David James,Lang, Jian-Ping
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p. 2374 - 2381
(2017/04/03)
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- 2,4,5-Trisubstituted thiazole derivatives as HIV-1 NNRTIs effective on both wild-type and mutant HIV-1 reverse transcriptase: Optimization of the substitution of positions 4 and 5
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In our previous work, novel 2,4,5-trisubstituted thiazole derivatives (TSTs) were synthesized, and their activities were evaluated against HIV-1 reverse transcriptase. Some interesting results were obtained, which led us to a new discovery regarding these TSTs. In the present study, 21 new 2,4,5-trisubstituted thiazole derivatives were rationally designed and synthesized as HIV-1 non-nucleoside reverse transcriptase inhibitors (NNRTIs) in accordance with our previous study. Among the synthesized target compounds, compounds 14, 16, 17, and 19 showed more potent inhibitory activities against HIV-1 with an IC50value of 0.010?μM. Compounds 4, 9, 10, 11, 13 and 16 were further tested on nine NNRTI-resistant HIV-1 strains, and all of these compounds exhibited inhibitory effects. A molecular docking study was conducted, and the results showed a consistent and stable binding mode for the typical compounds. These results have provided deeper insights and SAR of these types of NNRTIs.
- Xu, Zhongliang,Guo, Jiamei,Yang, Ying,Zhang, Mengdi,Ba, Mingyu,Li, Zhenzhong,Cao, Yingli,He, Ricai,Yu, Miao,Zhou, Hua,Li, Xiaoxi,Huang, Xiaoshan,Guo, Ying,Guo, Changbin
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supporting information
p. 309 - 316
(2016/08/04)
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- Bifunctional RuII-Complex-Catalysed Tandem C?C Bond Formation: Efficient and Atom Economical Strategy for the Utilisation of Alcohols as Alkylating Agents
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Catalytic activities of a series of functional bipyridine-based RuIIcomplexes in β-alkylation of secondary alcohols using primary alcohols were investigated. Bifunctional RuIIcomplex (3 a) bearing 6,6’-dihydroxy-2,2’-bipyridine (6DHBP) ligand exhibited the highest catalytic activity for this reaction. Using significantly lower catalyst loading (0.1 mol %) dehydrogenative carbon?carbon bond formation between numerous aromatic, aliphatic and heteroatom substituted alcohols were achieved with high selectivity. Notably, for the synthesis of β-alkylated secondary alcohols this protocol is a rare one-pot strategy using a metal–ligand cooperative RuIIsystem. Remarkably, complex 3 a demonstrated the highest reactivity compared to all the reported transition metal complexes in this reaction.
- Roy, Bivas Chandra,Chakrabarti, Kaushik,Shee, Sujan,Paul, Subhadeep,Kundu, Sabuj
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supporting information
p. 18147 - 18155
(2016/12/16)
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- Manganese-Catalyzed Hydrogen-Autotransfer C?C Bond Formation: α-Alkylation of Ketones with Primary Alcohols
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A novel catalytic hydrogen-autotransfer protocol for the atom-efficient α-alkylation of ketones with readily available alcohols is presented. The use of manganese complexes bearing non-innocent PNP pincer ligands enabled the functionalization of a broad range of valuable ketones, including 2-oxindole, estrone 3-methyl ether, and testosterone. Mechanistic investigations suggest the participation of an intramolecular amidate-assisted alcohol-dehydrogenation process.
- Pe?a-López, Miguel,Piehl, Patrick,Elangovan, Saravanakumar,Neumann, Helfried,Beller, Matthias
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supporting information
p. 14967 - 14971
(2016/11/25)
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- Cobalt-catalyzed intermolecular hydroacylation of olefins through chelation-assisted imidoyl C-H activation
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A low-valent cobalt catalyst generated from cobalt(II) bromide, a diphosphine ligand, and zinc powder promotes intermolecular hydroacylation of olefins using N-3-picolin-2-yl aldimines as aldehyde equivalents, which affords, upon acidic hydrolysis, ketone products in moderate to good yields with high linear selectivity. The reaction is applicable to styrenes, vinylsilanes, and aliphatic olefins as well as to various aryl and heteroaryl aldimines. The cobalt catalysis features a distinctively lower reaction temperature (60 °C) compared with those required for the same type of transformations catalyzed by rhodium complexes (typically 130-150°C).
- Yang, Junfeng,Seto, Yuan Wah,Yoshikai, Naohiko
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p. 3054 - 3057
(2015/05/20)
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- A novel transition metal-free conjugate reduction of α,β-unsaturated ketones with tosylhydrazine as a hydrogen source
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A novel and efficient method has been developed for the chemoselective conjugate reduction of α,β-unsaturated ketones with tosylhydrazine as a hydrogen source to the corresponding saturated ketones in moderate to good yields. The present protocol does not require the use of transition metal, and is efficient being applicable to a wide range of substrates (25 examples).
- Zhou, Xiaomeng,Li, Xiaokang,Zhang, Wei,Chen, Junmin
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supporting information
p. 5137 - 5140
(2015/02/19)
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- 2,4,5-Trisubstituted thiazole derivatives: A novel and potent class of non-nucleoside inhibitors of wild type and mutant HIV-1 reverse transcriptase
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Novel 2,4,5-trisubstituted thiazole derivatives (TSTs) were designed and synthesized as HIV-1 non-nucleoside reverse transcriptase inhibitors (NNRTIs). Among the thirty-eight synthesized target compounds, thirty TSTs showed potent inhibition against HIV-1 replication in wild type HIV-1 at submicromolar concentrations (from 0.046 to 9.59 μM). Compounds 21, 23 and 24 were also tested on seven NNRTI-resistant HIV-1 strains, and all exhibited inhibitory effects with fold changes in IC50 ranging from 2.6 to 111, which were better than those of nevirapine (15.6-fold-371-fold). Docking simulations of compound 24 revealed a reasonable mechanism for the binding mode, and three-dimensional quantitative structure activity relationship (3-DQSAR) studies on this novel series of TST further elucidated the structure-activity relationship (SAR). The results suggested the great potential of TSTs as a novel class of NNRTIs with antiviral efficacy and a good resistance profile.
- Xu, Zhongliang,Ba, Mingyu,Zhou, Hua,Cao, Yingli,Tang, Chaojun,Yang, Ying,He, Ricai,Liang, Yu,Zhang, Xuemei,Li, Zhenzhong,Zhu, Lihong,Guo, Ying,Guo, Changbin
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- C-C cross-coupling of primary and secondary benzylic alcohols using supported gold-based bimetallic catalysts
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Clean alcohol-alcohol cross-coupling: A clean and efficient one-pot direct C-C cross-coupling of equimolar amounts of primary and secondary alcohols by a facile hydrogen autotransfer pathway is achieved over a robust and easily recovered hydrotalcite-supported Au-Pd bimetallic catalyst system. A variety of primary and secondary alcohols have been selectively converted into the corresponding b-alkylated ketones in good yields.
- Liu, Xiang,Ding, Ran-Sheng,He, Lin,Liu, Yong-Mei,Cao, Yong,He, He-Yong,Fan, Kang-Nian
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p. 604 - 608
(2013/07/27)
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- Rhodium(I)-catalyzed arylation of β-chloro ketones and related derivatives through domino dehydrochlorination/conjugate addition
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Highly efficient arylations of β-chloro ketones and their ester and amide derivatives were achieved by means of domino dehydrochlorination/Rh(I)- catalyzed conjugate addition. In situ generated vinyl ketones and their analogues were identified as the reaction intermediates. The present synthetic protocol provides a concise route to (chiral) β-aryl ketones, esters, and amides. Copyright
- Jiang, Quanbin,Guo, Tenglong,Wang, Qingfu,Wu, Ping,Yu, Zhengkun
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supporting information
p. 1874 - 1880
(2013/07/19)
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- Aldehyde-catalyzed transition metal-free dehydrative β-alkylation of methyl carbinols with alcohols
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Different to the borrowing hydrogen strategy in which alcohols were activated by transition metal-catalyzed anaerobic dehydrogenation, the direct addition of aldehydes was found to be an effective but simpler way of alcohol activation that can lead to efficient and green aldehyde-catalyzed transition metal-free dehydrative C-alkylation of methyl carbinols with alcohols. Mechanistic studies revealed that the reaction proceeds via in situ formation of ketones by Oppenauer oxidation of the methyl carbinols by external aldehydes, aldol condensation, and Meerwein-Ponndorf-Verley (MPV)-type reduction of α,β-unsatutated ketones by substrate alcohols, affording the useful long chain alcohols and generating aldehydes and ketones as the by-products that will be recovered in the next condensation to finish the catalytic cycle. Copyright
- Xu, Qing,Chen, Jianhui,Liu, Quan
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supporting information
p. 697 - 704
(2013/04/10)
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- Synthesis of chromans via Pd-catalyzed alkene carboetherification reactions
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A new method for the construction of 2-substituted and 2,2-disubstituted chromans via Pd-catalyzed carboetherification reactions between aryl/alkenyl halides and 2-(but-3-en-1-yl)phenols is described. These reactions effect formation of a C-O bond and a C-C bond to afford the chroman products in good yield, and also provide stereoselective access to tricyclic chroman derivatives.
- Ward, Amanda F.,Xu, Yan,Wolfe, John P.
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supporting information; experimental part
p. 609 - 611
(2012/01/14)
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- RuHCl(CO)(PPh3)3-catalyzed R-alkylation of ketones with primary alcohols
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The α-alkylation reaction of ketones with primary alcohols to give α-alkylated ketones was achieved using RuHCl(CO)(PPh3) 3 as a catalyst in the presence of Cs2CO3 as a base. This reaction proceeds via an aldol condensation of ketones with aldehydes, formed via transfer dehydrogenation of alcohols, to give α,β-unsaturated ketones, which then undergo transfer hydrogenation with primary alcohols to give R-alkylated ketones and aldehydes, the latter of which participate in the next catalytic cycle. While the reaction of aliphatic primary alcohols was sluggish compared with that of benzylic alcohols, a catalytic amount of 1,10-phenanthroline was found to promote the alkylation dramatically.
- Kuwahara, Takashi,Fukuyama, Takahide,Ryu, Ilhyong
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supporting information
p. 4703 - 4705,3
(2020/09/16)
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- Arenediazonium o-benzenedisulfonimides in Heck-type arylation of allylic alcohols
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Arenediazonium o-benzenedisulfonimides were reacted with primary and secondary allylic alcohols. The reactions, carried out in aqueous ethanol in the presence of palladium(II) acetate as precatalyst and sodium hydrogen carbonate as base, gave the arylation products with good overall conversion. In all cases, the major products were the β-arylated carbonyl derivatives. The o-benzene-disulfonimide was recovered in high yield from all the reactions, and it was recycled for the preparation of other salts. Georg Thieme Verlag Stuttgart.
- Barbero, Margherita,Cadamuro, Silvano,Dughera, Stefano
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p. 3443 - 3452
(2008/02/12)
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- Chemoselective Reduction of α,βUnsaturated Aldehydes, Ketones, Carboxylic Acids, and Esters with Nickel Boride in Methanol-Water
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A facile procedure for the conjugate reduction of α,β -unsaturated aldehydes, ketones, carboxylic acids, and esters is reported with nickel boride generated in situ from NiCl2·6H 2O/NaBH4 in methanol-water at ambient temperature.
- Khurana, Jitender Mohan,Sharma, Purnima
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p. 549 - 552
(2007/10/03)
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- The Chemistry of Aryllead(IV) Tricarboxylates. Reaction with Silyl Enol Ethers
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The trimethylsilyl enol ether of acetophenone (1) and p-methoxyphenyllead triacetate (2) react to give (p-methoxyphenyl)phenacyllead(IV) diacetate (4) in high yield.This plumbation reaction has been studied for a number of ketone trimethylsilyl enol ethers and aryllead triacetates, and it would appear that it is probably limited to aryl ketone trimethylsilyl enol ethers.The trifluoroacetic acid catalysed break down of these α-plumbated ketones to substituted deoxybenzoins has been examined in considerable detail.The thermal decomposition of one of the lead compounds to a deoxybenzoin derivative has also been examined.
- Bell, Craig H.,Pinhey, John T.,Sternhell, Sever
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p. 2237 - 2245
(2007/10/02)
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