- 8-Methoxyquinoline based turn-on metal fluoroionophores
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Novel turn-on fluoroionophores 2 and 3 based on highly fluorescent 8-methoxyquinoline were developed in which a sequential singlet-singlet energy transfer, ISC, and triplet-triplet energy transfer occurred leading to a fluorescence 'off' state. They showe
- Zhang, Han,Wang, Qiang-Li,Jiang, Yun-Bao
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- Oxybromination of ethynylbenzene catalysed by molybdenum complexes in organic solvent and in ionic liquids
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The molybdenum(VI)-catalysed oxybromination of ethynylbenzene was performed with hydrogen peroxide as oxidant and potassium bromide as source of bromine, in a two-phase water/solvent system, where solvent was either dichloromethane or an ionic liquid. The selectivity was toward 1,2-dibromostyrene when performed in water/dichloromethane. In ionic liquids better yields and shorter reaction times were obtained that, together with the complete ethynylbenzene conversion and the preferred formation of α,α-dibromoacetophenone, make the reaction synthetically useful.
- Conte, Valeria,Floris, Barbara,Galloni, Pierluca,Silvagni, Adriano
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- Dichloroacetophenone Derivatives: A Class of Bioconjugation Reagents for Disulfide Bridging
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A mild and biocompatible method for the construction of disulfide bridging in peptides using dichloroacetophenone derivatives is developed. This method is highly selective (chemo, diastereo, regio, etc.) and atom economic and works under biocompatible reaction conditions (metal-free, water, pH 7, rt, etc.).
- Wu, Liu-Hai,Zhou, Shuguang,Luo, Qun-Feng,Tian, Jie-Sheng,Loh, Teck-Peng
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- Access to α,α-dihaloacetophenones through anodic C[dbnd]C bond cleavage in enaminones
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We have developed a method to synthesize α,α-dihaloketones under electrochemical conditions. In this reaction, the Cl- or Br- is oxidized to Cl2 or Br2 at the anode, which undergoes two-step addition reactions with the N,N-dimethyl enaminone, and finally breaks C[dbnd]C of the N,N-dimethyl enaminone to generate α,α-dihaloketones. The electrosynthesis reaction can be conveniently carried out in an undivided electrolytic cell at room temperature. In addition, various functional groups are compatible with this green protocol which can be applied simultaneously to the gram scale without significantly lower yield.
- Zhang, Zhenlei,Yang, Jiusi,Wu, Kairui,Yu, Renjie,Bu, Jiping,Huang, Zijun,Li, Shaoke,Ma, Xiantao
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- Transition-metal- and phosphorus-free electrophilic trifluoromethylthiolation of indoles with sodium trifluoromethanesulfinates in ionic liquids
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An acid-promoted protocol has been developed to achieve the transition-metal- and phosphorus-free electrophilic trifluoromethylthiolation of indoles using sodium trifluoromethanesulfinates in an imidazolium-based ionic liquid ([Hmim]Br). [Hmim]Br not only acts as a recyclable solvent, but also as the reductant in this transformation. The advantages of this chemistry include simple operation, use of a recyclable solvent, avoidance of transition-metal and phosphorus, and gram-scale synthesis.
- Wang, Fei,Lu, Guo-Ping,Lin, Yamei
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- Flexible on-site halogenation paired with hydrogenation using halide electrolysis
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Direct electrochemical halogenation has appeared as an appealing approach in synthesizing organic halides in which inexpensive inorganic halide sources are employed and electrical power is the sole driving force. However, the intrinsic characteristics of direct electrochemical halogenation limit its reaction scope. Herein, we report an on-site halogenation strategy utilizing halogen gas produced from halide electrolysis while the halogenation reaction takes place in a reactor spatially isolated from the electrochemical cell. Such a flexible approach is able to successfully halogenate substrates bearing oxidatively labile functionalities, which are challenging for direct electrochemical halogenation. In addition, low-polar organic solvents, redox-active metal catalysts, and variable temperature conditions, inconvenient for direct electrochemical reactions, could be readily employed for our on-site halogenation. Hence, a wide range of substrates including arenes, heteroarenes, alkenes, alkynes, and ketones all exhibit excellent halogenation yields. Moreover, the simultaneously generated H2at the cathode during halide electrolysis can also be utilized for on-site hydrogenation. Such a strategy of paired halogenation/hydrogenation maximizes the atom economy and energy efficiency of halide electrolysis. Taking advantage of the on-site production of halogen and H2gases using portable halide electrolysis but not being suffered from electrolyte separation and restricted reaction conditions, our approach of flexible halogenation coupled with hydrogenation enables green and scalable synthesis of organic halides and value-added products.
- Shang, Xiao,Liu, Xuan,Sun, Yujie
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supporting information
p. 2037 - 2043
(2021/03/26)
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- Solvent-free preparation of α,α-dichloroketones with sulfuryl chloride
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An efficient and facile method is reported for the synthesis of a series of α,α-dichloroketones. The direct dichlorination of methyl ketones and 1,3-dicarbonyls using an excess amount of sulfuryl chloride affords the corresponding gem-dichloro compounds in moderate to excellent yields. Moreover, the protocol features high yields, broad substrate scope, and simple reaction conditions without using any catalysts and solvents.
- Tu, Dewei,Luo, Juan,Jiang, Wengao,Tang, Qiang
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supporting information
(2021/09/15)
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- TEMPO-Regulated Regio- and Stereoselective Cross-Dihalogenation with Dual Electrophilic X+ Reagents
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A TEMPO catalyzed cross-dihalogenation reaction was established via redox-regulation of the otherwise complex system of dual electrophilic X+ reagents. Formally, the ICl, BrCl, I2 and Br2 were generated in-situ, which enabled high regio- or stereoselective access to a myriad of iodochlorination, bromochlorination and homo-dihalogenation products with a wide spectrum of functionalities. With its mild conditions and operational simplicity, this method could enable wide applications in organic synthesis, which was exemplified by divergent synthesis of two pharmaceuticals. Detailed mechanistic investigations via radical clock reaction, pinacol ring expansion and Hammett experiments were conducted, which confirmed the intermediacy of halonium ion. In addition, a dynamic catalytic model based on the versatile catalytic role of TEMPO was proposed to explain the selective outcomes.
- Kong, Yi,Cao, Tongxiang,Zhu, Shifa
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supporting information
p. 3004 - 3010
(2021/08/23)
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- Electrochemical Oxidative Functionalization of Arylalkynes: Access to α,α-Dibromo Aryl Ketones
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A general and effective protocol to synthesize α,α-dibromo aryl ketones has been developed via an electrochemical oxidative method. The reaction proceeds smoothly at room temperature in an undivided cell without the addition of external oxidants. In the reaction process, LiBr acts as both bromine source and supporting electrolyte. This electrooxidation strategy has good substrate applicability and functional group compatibility. Moreover, the reaction could be scaled up efficiently in a continuous flow cell. The target product could undergo further functionalization for the synthesis of some useful heterocyclic compounds. (Figure presented.).
- Wang, Dan,Wan, Zhaohua,Zhang, Heng,Lei, Aiwen
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supporting information
p. 1022 - 1027
(2020/12/31)
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- Facile Approach to Geminal HeterodihalogenationOne-Pot Synthesis of α-Bromo-α-Chloro Ketones
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An efficient and practical protocol for the geminal heterodihalogenation of methyl ketones by using readily available dimethyl sulfoxide and a combination of HCl and HBr is reported. Control experiments suggested that the acidity of the solution, as well as the oxidizing ability and nucleophilicity of the dimethyl sulfoxide might work cooperatively in ensuring the success of the tandem substitution. Its operational simplicity, easy accessibility, and mild oxidative conditions suggest that the present strategy might be useful for the assembly of bromochloromethyl functional groups in drug discovery.
- Bian, Ming,Tang, Dong-Min,Zhou, Jin-Feng
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- α,α-Dibromoketone precursors in the synthesis of some new thiazole derivatives: Thiazol-2-yl hydrazonobutanoates, thiazol-2-yl pyrazole-4-carboxylates and acids
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In the present study, α,α-dibromoacetophenones are used as efficient precursors for the facile synthesis of several new hydrazonothiazoles, ethyl 3-((4-arylthiazol-2-yl)hydrazono)butanoates, which undergo Vilsmeier-Haack cyclization to obtain thiazolylpyrazole esters, ethyl 3-methyl-1-(4-arylthiazol-2-yl)-1H-pyrazole-4-carbxylates, basic hydrolysis of which gives the corresponding acids, 3-methyl-1-(4-arylthiazol-2-yl)-1H-pyrazole-4-carbxylic acids. All these compounds are tested for antibacterial activity against Gram-positive bacteria Staphylococcus aureus and Bacillus subtilis; Gram-negative bacteria Escherichia coli and Pseudomonas aeruginosa and antifungal activity against Saccharomyces cerevisiae and Candida albicans.
- Joshi, Radhika,Kiran, Vijay,Pundeer, Rashmi
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supporting information
(2020/03/04)
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- Selective Debromination of α,α,α-Tribromomethylketones with HBr–H2O Reductive Catalytic System
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A debromination of α,α,α-tribromomethylketones is developed for chemoselective synthesis of α-mono- and α,α-dibromomethylketones with high selectivity under H2O–HBr reductive conditions. This method offers an efficient and direct way to synthesize α-mono or α,α-dibromomethylketone compounds in high to excellent yields through the process of HBr self-circulation in water.
- Cheng, Zhao,Guo, Hongmei,Huang, Guozheng,Rexit, Abulikemu Abudu,Wang, Hui,Zheng, Meng-Xia
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p. 6455 - 6458
(2020/10/21)
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- Method for preparing alpha,alpha-dihalogenated acetophenone compound
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The invention belongs to the technical field of organic synthesis and in particular relates to a method for preparing an alpha,alpha-dihalogenated acetophenone compound. The preparation method provided by the invention comprises the following steps: in an alcohol solvent, enabling nitroalkenes, electrophilic halogen reagents and sodium hydride to react at 55-65 DEG C under a heating condition for5-10 hours, cooling the components to the room temperature, adding a diluted acid solution, and performing continue stirring for 2-5 hours, so as to obtain a target compound, namely alpha,alpha-dihalogenated acetophenone. The method for preparing the alpha,alpha-dihalogenated acetophenone compound, which is provided by the invention, is simple and efficient, mild in condition, easy in raw materialobtaining, green and environment-friendly and simple and convenient to operate, and as a synthesis intermediate, the obtained alpha,alpha-dihalogenated acetophenone compound has the potential of being widely used in fields such as medicine chemical engineering.
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Paragraph 0027-0032
(2020/02/04)
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- Switchable Synthesis of α,α-Dihalomethyl and α,α,α-Trihalomethyl Ketones by Metal-Free Decomposition of Enaminone C=C Double Bond
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The novel free radical-based cleavage of the enaminone C=C double bond is realized by using N-halosuccinimides (NXS) in the presence of benzoyl peroxide (BPO) with mild heating, enabling the tunable synthesis of α,α-dihalomethyl ketones and α,α,α-trihalomethyl ketones under different reaction conditions. The formation of these divergent products involving featured C=C double bond cleavage requires no any metal reagent, and represents one more practical example on the synthesis of poly halogenated methyl ketones via the functionalization of carbon?carbon bond. (Figure presented.).
- Liu, Yunyun,Xiong, Jin,Wei, Li,Wan, Jie-Ping
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supporting information
p. 877 - 883
(2020/01/24)
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- Electrochemical synthesis of α,α-dihaloacetophenones from terminal alkyne derivatives
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By virtue of electrochemistry, a series of α,α-dihaloacetophenones were easily obtained with good to excellent yields. This electrochemical procedure was taken in a divided cell with constant current in aqueous media. The reaction can be carried out smoothly at room temperature under metal and oxidant free condition, which provides an eco-friendly synthesis for the α,α-dihaloacetophenone derivatives.
- Li, Zhibin,Sun, Qi,Qian, Peng,Hu, Kangfei,Zha, Zhenggen,Wang, Zhiyong
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supporting information
p. 1855 - 1858
(2020/03/10)
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- Electrochemical Oxidative Oxydihalogenation of Alkynes for the Synthesis of α,α-Dihaloketones
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An electrochemical oxydihalogenation of alkynes has been developed for the first time. Using this sustainable protocol, a variety of α,α-dihaloketones can be prepared with readily available CHCl3, CH2Cl2, ClCH2CH2Cl, and CH2Br2 as the halogen source under electrochemical conditions at room temperature.
- Meng, Xiangtai,Zhang, Yu,Luo, Jinyue,Wang, Fei,Cao, Xiaoji,Huang, Shenlin
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supporting information
p. 1169 - 1174
(2020/02/04)
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- Iron-catalyzed acylation-functionalization of unactivated alkenes with aldehydes
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Herein, an iron-catalyzed acylation-functionalization of unactivated alkenes with aldehydes via distal group ipso-migration is reported. This strategy overcame the energy barrier and reversibility in the difunctionalization of unactivated alkenes with nuc
- Tian, Tian,Wang, Xin,Lv, Leiyang,Li, Zhiping
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supporting information
p. 14637 - 14640
(2020/12/02)
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- Application of poly(vinylphenyltrimethylammonium tribromide) resin as an efficient polymeric brominating agent in the α-bromination and α-bromoacetalization of acetophenones
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The applications of a new supported tribromide reagent based on poly(vinylbenzyltrimethylammonium hydroxide) resin (Amberlite 717) were reported. This supported tribromide resin was used directly in α-bromination and α-bromoacetalization of acetophenones without any other catalyst under mild conditions. The effects of solvents and the amount of the supported tribromide resin on the reactions were investigated. Under the optimal conditions, most of α-bromo and α-bromoacetal of acetophenones were selectively obtained in excellent yields.
- Han, Bingbing,Zheng, Zubiao,Zheng, Dongcheng,Zhang, Lei,Cui, Peng,Shi, Jianjun,Li, Changjiang
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supporting information
p. 2512 - 2520
(2019/07/04)
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- Synthesis of Ti-Al binary oxides and their catalytic application for C-H halogenation of phenols, aldehydes and ketones
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Traditional C–H halogenation of organic compounds often requires corrosive agent or harsh condition, and current researches are focused on the use of noble metals as catalyst. In order to give an efficient, benign, activity-adjustable and cost-effective system for halogenation, a series of Ti-Al mixed oxides are prepared as catalyst through sol-gel in this work. Characterizations reveal all catalysts contain more aluminum than titanium, but preparative conditions affect their composition and crystallinity. Monitoring of particle size, zeta potential and UV–vis of preparative solution reveals that formation of catalyst colloids undergoes chemical reaction, affecting catalyst morphology. In halogenation, all catalysts show moderate to high activities, copper chloride proves to be an effective halogen source rather than sodium chloride. The chlorination and bromination are better than iodization, phenol and ketone appear to be more appropriate substrates than aldehyde. Additionally, oxide backbone of catalyst is more durable than its organic components during recycling. This study may provide new catalytic materials for progress of C–H activation.
- Su, Peigen,Fan, Chao,Yu, Heng,Wang, Wanqin,Jia, Xin,Rao, Qifan,Fu, Chenxi,Zhang, Donghua,Huang, Benhua,Pan, Cheng,Zheng, Aqun,Sun, Yang
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- Alkyl Halides via Visible Light Mediated Dehalogenation
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Net selective bromination and chlorination of activated C-H bonds can be effected in generally high yield via a simple perhalogenation/dehalogenation sequence. The photochemical reductions require no photocatalyst, relying instead on the formation of an electron donor-acceptor complex of the substrate and reductant, or alternatively autophotocatalysis. Some reactions proceed despite any apparent photon absorption, serving as a cautionary tale for other photochemical reactions involving amines. Mechanistic experiments provide an explanation for this observation.
- Rathnayake, Manjula D.,Weaver, Jimmie D.
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supporting information
p. 9681 - 9687
(2019/11/28)
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- Visible-light-promoted oxidative halogenation of alkynes
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In nature, halogenation promotes the biological activity of secondary metabolites, especially geminal dihalogenation. Related natural molecules have been studied for decades. In recent years, their diversified vital activities have been explored for treating various diseases, which call for efficient and divergent synthetic strategies to facilitate drug discovery. Here we report a catalyst-free oxidative halogenation achieved under ambient conditions (halide ion, air, water, visible light, room temperature, and normal pressure). Constitutionally, electron transfer between the oxygen and halide ion is shuttled via simple conjugated molecules, in which phenylacetylene works as both reactant and catalyst. Synthetically, it provides a highly compatible late-stage transformation strategy to build up dihaloacetophenones (DHAPs).
- Li, Yiming,Mou, Tao,Lu, Lingling,Jiang, Xuefeng
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supporting information
p. 14299 - 14302
(2019/12/02)
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- Carbonyl dibromo compound, as well as preparation method and application thereof
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The invention belongs to the technical field of synthetic chemistry, and discloses a carbonyl dibromo compound, as well as a preparation method and an application thereof. The carbonyl dibromo compound has a chemical structural general formula as shown in the specification, wherein R is aryl, substituted aryl, heteroaryl, substituted heteroaryl, paraffin, substituted alkyl or silicyl, wherein thesubstituent group of the substituted aryl, substituted heteroaryl and substituted alkyl is more than one of halogen, alkyl, halogenated alkyl, alkoxy, nitryl, hydroxy, cyan, ester, carbonyl or amide;the heteroaryl is an aromatic ring containing nitrogen, oxygen or sulfur or derivatives thereof. According to the carbonyl dibromo compound, an alkyne compound and sodium bromide are used as raw materials, a high-iodine reagent is used as a catalyst and oxidant, the carbonyl dibromo compound is generated from the alkyne compound. The method has the advantages of mild reaction condition, no heatingrequirement, simple operation steps, high selectivity and high yield, and is safe, reliable and environment-friendly.
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Paragraph 0046-0048
(2019/03/08)
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- Substituent Effect in the Synthesis of α,α-Dibromoketones, 1,2-Dibromalkenes, and 1,2-Diketones from the Reaction of Alkynes and Dibromoisocyanuric Acid
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Internal alkynes reacted with dibromoisocyanuric acid/H2O to afford α,α-dibromoketone and 1,2-diketone derivatives. Diarylalkynes with activating groups provided 1,2-diketone derivatives as the major products, whereas diarylalkynes with a non-activating group or alkylarylalkynes gave α,α-dibromoketone derivatives as the major products. In addition, diarylalkynes with deactivating groups provided 1,2-dibromoalkenes. The reaction was conducted at room temperature and showed good yields in most cases. Reaction pathways have been proposed on the basis of experimental observations and density functional theory (DFT) calculations. (Figure presented.).
- Cho, Eunjeong,Jayaraman, Aravindan,Lee, Junseong,Ko, Kyoung Chul,Lee, Sunwoo
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p. 1846 - 1858
(2019/03/07)
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- Copper Nitrate-Mediated Selective Difunctionalization of Alkenes: A Rapid Access to β-Bromonitrates
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A regioselective copper nitrate-mediated difunctionalization of alkenes has been developed for the rapid synthesis of β-bromonitrates, where copper nitrate is used as an ideal nitrooxy source for the first time and the products will find many applications in organic synthesis as versatile synthons. Different from the general reports that copper nitrate acts as the nitro source, the given protocol provides a direct access to functionalized nitrates, with operational simplicity, good functional group tolerance and a wide substrate scope. (Figure presented.).
- Gao, Mingchun,Zhou, Kaijing,Xu, Bin
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supporting information
p. 2031 - 2036
(2019/03/28)
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- A Highly Efficient Method for the Bromination of Alkenes, Alkynes and Ketones Using Dimethyl Sulfoxide and Oxalyl Bromide
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The pairing of DMSO and oxalyl bromide is reported as a highly efficient brominating reagent for various alkenes, alkynes and ketones. This bromination approach demonstrates remarkable advantages, such as mild conditions, low cost, short reaction times, provides excellent yields in most cases and represents a very attractive alternative for the preparation of dibromides and α-bromoketones.
- Ding, Rui,Li, Jiaqi,Jiao, Wenyi,Han, Mengru,Liu, Yongguo,Tian, Hongyu,Sun, Baoguo
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p. 4325 - 4335
(2018/11/21)
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- Highly efficient recyclable sol gel polymer catalyzed one pot difunctionalization of alkynes
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Amino-bridged gel polymer P1 was discovered to catalyze alkyne halo-functionalization in excellent yields, regioselectivity, functional group compatibility, and recyclability. We have observed that both aromatic and aliphatic alkynes can be converted to α,α-dihalogenated ketones in the presence of polymer P1 under metal-free conditions at room temperature within a short reaction time.
- Domena, Justin,Chong, Carlos,Johnson, Qiaxian R.,Chauhan, Bhanu P. S.,Xing, Yalan
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supporting information
(2018/08/17)
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- A H2O2/HBr system-several directions but one choice: oxidation-bromination of secondary alcohols into mono- or dibromo ketones
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In this work we found that a H2O2-HBr(aq) system allows synthesis of α-monobromo ketones and α,α′-dibromo ketones from aliphatic and secondary benzylic alcohols with yields up to 91%. It is possible to selectively direct the process toward the formation of mono- or dibromo ketones by varying the amount of hydrogen peroxide and hydrobromic acid. The convenience of application, simple equipment, multifaceted reactivity, and compliance with green chemistry principles make the application of the H2O2-HBr(aq) system very attractive in laboratories and industry. The proposed oxidation-bromination process is selective in spite of known properties of ketones to be oxidized by the Baeyer-Villiger reaction or peroxidated with the formation of compounds with the O-O moiety in the presence of hydrogen peroxide and Bronsted acids.
- Nikishin, Gennady I.,Kapustina, Nadezhda I.,Sokova, Liubov L.,Bityukov, Oleg V.,Terent'ev, Alexander O.
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p. 28632 - 28636
(2018/08/31)
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- Preparation method of alpha, alpha-dibromoketone
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The invention belongs to the field of preparation of fine chemical products and synthesis of pharmaceutical intermediates and relates to a preparation method of novel alpha, alpha-dibromoketone, in particular to a method for converting olefin into alpha, alpha-dibromoketone by use of dibromohydantoin or N-bromosuccinimide. Compared with the reported methods, the method has the advantages that rawmaterials are easy to obtain and low in cost, used reagents have smaller toxicity, and the method has greater cost and environmental protection advantages and wide application prospects.
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Paragraph 0021-0023
(2018/04/21)
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- Micelle-Enabled Photoassisted Selective Oxyhalogenation of Alkynes in Water under Mild Conditions
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Using micelles of FI-750-M, visible light, photocatalysts, and inexpensive halogenating reagents, such as N-bromosuccinimide and N-chlorosuccinimde, selective oxyhalogenations of alkynes were achieved in water under very mild conditions. No halogenation at the aromatic rings was detected, and control experiments revealed the radical pathway. The easily conducted protocol exhibited high reproducibility, was readily adjusted to gram scale, and allowed for recycling of reaction medium and catalyst.
- Finck, Lucie,Brals, Jeremy,Pavuluri, Bhavana,Gallou, Fabrice,Handa, Sachin
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p. 7366 - 7372
(2018/07/29)
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- One-pot syntheses of α,α-dibromoacetophenones from aromatic alkenes with 1,3-dibromo-5,5-dimethylhydantoin
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A novel method for the preparation of α,α-dibromoacetophenones from aromatic alkenes was reported. This procedure was mediated by 1,3-dibromo-5,5-dimethylhydantoin, which served as bifunctional reagent, proceeding oxidation and bromination in one-pot.
- Wu, Ping,Xu, Senhan,Xu, Hao,Hu, Haiyan,Zhang, Wei
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supporting information
p. 618 - 621
(2017/01/25)
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- Directing group assisted copper-mediated aroylation of phenols using 2-bromoacetophenones
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A new directing group assisted method for the synthesis of aryl esters is described. In this Cu(ii)-mediated reaction, 2-formylphenols and 2-acetylphenols are easily converted into aryl esters via treatment with a new aroylating agent 2-bromoacetophenone.
- Baruah, Swagata,Borthakur, Somadrita,Gogoi, Sanjib
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supporting information
p. 9133 - 9135
(2017/08/17)
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- High-Potency Phenylquinoxalinone Cystic Fibrosis Transmembrane Conductance Regulator (CFTR) Activators
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We previously identified phenylquinoxalinone CFTRact-J027 (4) as a cystic fibrosis transmembrane conductance regulator (CFTR) activator with an EC50 of ~200 nM and demonstrated its therapeutic efficacy in mouse models of constipation. Here, structure-activity studies were done on 36 synthesized phenylquinoxalinone analogs to identify compounds with improved potency and altered metabolic stability. Synthesis of the phenylquinoxalinone core was generally accomplished by condensation of 1,2-phenylenediamines with substituted phenyloxoacetates. Structure-activity studies established, among other features, the privileged nature of a properly positioned nitro moiety on the 3-aryl group. Synthesized analogs showed improved CFTR activation potency compared to 4 with EC50 down to 21 nM and with greater metabolic stability. CFTR activators have potential therapeutic indications in constipation, dry eye, cholestatic liver diseases, and inflammatory lung disorders.
- Son, Jung-Ho,Zhu, Jie S.,Phuan, Puay-Wah,Cil, Onur,Teuthorn, Andrew P.,Ku, Colton K.,Lee, Sujin,Verkman, Alan S.,Kurth, Mark J.
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p. 2401 - 2410
(2017/04/03)
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- Method for selective bromination of phenyl alkyl ketone derivatives or phenyl alkyl alcohol derivatives
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The present invention refers to phenyl alkyl ketone derivatives or phenyl alkyl alcohol for the preparation of bromide to method are disclosed. Bromination reaction which is an expensive raw material without said number [...] cap, a photocuring liquid bromine (Br) toxic substances toxic to all the remaining wastewater has been exhausted not environment-friendly method are disclosed. In addition, regioselective bromination reaction so as to control, high yield can be undesired compounds. (by machine translation)
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Paragraph 0073-0077
(2018/02/27)
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- Reaction of trihaloisocyanuric acids with alkynes: An efficient methodology for the preparation of β-haloenol acetates
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The reaction between trihaloisocyanuric acids and alkynes in the presence of acetic acid provides an efficient methodology for preparation of β-haloenol acetates in yields ranging from 34 to 94%, depending on the halogen and alkynes used. This methodology provides an alternative to typical procedures, which usually employ metal catalysis and are limited to terminal alkynes.
- Crespo, Livia T.C.,Nogueira, Geisa P.,De Mattos, Marcio C.S.,Esteves, Pierre M.
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p. 205 - 214
(2018/02/07)
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- α,α-Alkylation-Halogenation and Dihalogenation of Sulfoxonium Ylides. A Direct Preparation of Geminal Difunctionalized Ketones
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A one-pot alkylation–halogenation of ketosulfoxonium ylides in the presence of alkyl halides is described. The method furnishes several gem-difunctionalized haloketones (an alkyl and F, Cl, Br, or I) in good yields. Replacing alkyl halides with a mixture of electrophilic halogen species and various halide anions led to gem-dihalogenated ketones containing a combination of the same or two different halogens. Kinetic isotopic effects as well as reaction kinetic experiments give insight to the mechanism of these reactions.
- Gallo, Rafael D. C.,Ahmad, Anees,Metzker, Gustavo,Burtoloso, Antonio C. B.
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p. 16980 - 16984
(2017/11/27)
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- Water-controlled selective preparation of α-mono or α,α′-dihalo ketones: Via catalytic cascade reaction of unactivated alkynes with 1,3-dihalo-5,5-dimethylhydantoin
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The control of a reaction that can produce multiple products from the same starting material is a highly attractive and challenging concept in organic synthesis. An efficient protocol for the selective synthesis of α-mono or α,α′-dihalo ketones via a water-controlled three-component thiourea-catalyzed cascade reaction of unactivated alkynes, 1,3-dihalo-5,5-dimethylhydantoin and water has been developed. α-Monohaloketones were obtained in aqueous acetone at 45 °C; conversely, α,α′-dihalo ketones were formed with pure water as the sole solvent at room temperature.
- Wu, Chao,Xin, Xiu,Fu, Zhi-Min,Xie, Long-Yong,Liu, Kai-Jian,Wang, Zheng,Li, Wenyi,Yuan, Zhi-Hui,He, Wei-Min
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p. 1983 - 1989
(2017/06/09)
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- One-pot dichlorinative deamidation of primary β-ketoamides
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An approach to the dichlorinative deamidation of primary β-ketoamides through ketonic cleavage is described, and a series of α,α-dichloroketones were furnished mostly in the presence of TEMPO. Based on control experiments, a mechanism involving tandem dichlorination and deamidation is proposed to interpret the observed reactivity.
- Zheng, Congke,Zhang, Xiaohui,Ijaz Hussain, Muhammad,Huang, Mingming,Liu, Qing,Xiong, Yan,Zhu, Xiangming
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p. 574 - 577
(2017/01/16)
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- AuIII-Catalyzed Formation of α-Halomethyl Ketones from Terminal Alkynes
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A AuIII-catalyzed synthesis of α-halomethyl ketones from terminal alkynes was developed. This approach features excellent functional group compatibility and good yields for both aromatic and aliphatic terminal alkynes. The resulting α-halomethyl ketones were used to prepare heterocyclic indolizine structures. The plausible mechanism of the one-pot reaction is proposed.
- Xing, Yalan,Zhang, Ming,Ciccarelli, Sarah,Lee, John,Catano, Bryant
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supporting information
p. 781 - 785
(2017/02/15)
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- CoFe2O4–SiO2–SO3H nanocomposite as a magnetically recoverable catalyst for oxidative bromination of alkynes
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A hybrid catalyst has been prepared by incorporating sulfonic acid onto cobalt ferrite magnetic nanoparticles. The catalyst was successfully applied for rapid (20 min) synthesis of α,α-dibromoketones directly from alkynes and NBS. The reaction works well in the presence of 10 wt% of the catalyst at room temperature to produce the desired products in high yield. The catalyst could be recovered using an external magnet and reused without appreciable change in activity.
- Dutta, Mintu Maan,Rajbongshi, Kamal Krishna,Phukan, Prodeep
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p. 2330 - 2341
(2017/11/15)
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- Ultrasound-assisted tandem reaction of alkynes and trihaloisocyanuric acids by thiourea as catalyst in water
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With water as the sole solvent, a green and efficient method has been developed for the synthesis of various α,α-dihaloketones via ultrasound assisted p-tolylthiourea catalyzed tandem reaction of alkynes with trihaloisocyanuric acids. This synthetic route
- Zhang, Xingyu,Wu, Yundong,Zhang, Ya,Liu, Huilan,Xie, Ziyu,Fu, Shengmin,Liu, Fang
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p. 4513 - 4518
(2017/07/10)
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- α,α-dibromoketones as useful precursors in organic synthesis: A simple and efficient synthesis of 2,4-diaryl- 1,2,3-triazoles via oxidative cyclization of bisphenylhydrazones
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α,α-Dibromoacetophenones (1a-1f) on reaction with phenylhydrazine afford corresponding arylglyoxal bisphenylhydrazones (2a-2f). The oxidation of bishydrazones 2a-2f by using copper(II) chloride in acetic acid leads to intramolecular cyclization with the formation of 2,4-diaryl-1,2,3-triazoles (3a-3f). The method for the conversion 1 → 3 has been simplified by developing one-pot procedure without isolation of intermediates 2.
- Arora, Loveena,Sharma, Nisha,Kapoor, Jitander K.
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p. 291 - 296
(2019/01/18)
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- Direct Transformation of Ethylarenes into Primary Aromatic Amides with N -Bromosuccinimide and I2-Aqueous NH3
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A variety of ethylarenes were converted into the corresponding primary aromatic amides in good yields via treatment with N-bromosuccinimide in the presence of a catalytic amount of 2,2′-azobis(isobutyronitrile) in a mixture of ethyl acetate and water, acetonitrile and water, or chloroform and water, followed by reaction with molecular iodine and aq NH3 in one pot. It was found that aryl α-bromomethyl ketones and/or aryl methyl ketones were formed at the first reaction step and their iodoform-type reaction occurred at the second reaction step to provide primary aromatic amides. The present reaction is a useful and practical transition-metal-free method for the preparation of primary aromatic amides from ethylarenes. (Chemical Equation Presented).
- Shimokawa, Shohei,Kawagoe, Yuhsuke,Moriyama, Katsuhiko,Togo, Hideo
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supporting information
p. 784 - 787
(2016/03/01)
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- Efficient and simple preparation of functionalized 1,1-dibromoenol phosphates
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The preparation of functionalized 1,1-dibromoalkenyl phosphates is described. The protocol developed for their preparation is based on the generation of enolates from α,α-dibromoketones followed by a reaction with dialkyl chlorophosphates. The procedure t
- Kotek, Vladislav,Polk, Peter,Tobrman, Tom
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p. 405 - 412
(2016/02/16)
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- Synthesis of 2-Keto(hetero)aryl Benzox(thio)azoles through Base Promoted Cyclization of 2-Amino(thio)phenols with α,α-Dihaloketones
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An interesting base-promoted protocol for the synthesis of 2-keto(hetero)aryl benzox(thi)azoles has been developed. Starting from commercially available 2-amino(thio)phenols and α,α-dihaloketones, moderate to good yields of the corresponding heterocycles can be achieved. Notably, only EtNH2 was required as the promoter here, and the reaction can be easily performed on a large scale.
- Jiang, Jun,Zou, Huaxu,Dong, Qizhi,Wang, Ruijia,Lu, Linghui,Zhu, Yonggang,He, Weimin
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- TsNBr2mediated oxidative functionalization of alkynes
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A new approach has been developed for oxidative transformation of alkynes by controlled manipulation of TsNBr2mediated process. Alkynes could be readily converted to ketones and α-bromoketones via an oxybromination–debromination sequence. When alkynes are treated successively with TsNBr2, KI and Na2SO3in a mixture of acetone and water at room temperature, corresponding ketones were obtained. On the other hand, treatment of alkynes with TsNBr2and Na2SO3in a mixture of ethyl acetate, acetone and water at room temperature could produce corresponding α-bromoketones. 1-Bromoalkynes could also be synthesized from corresponding alkynes within a very short time using TsNBr2at room temperature. In all cases, excellent yields of corresponding products are obtained.
- Rajbongshi, Kamal Krishna,Hazarika, Debojit,Phukan, Prodeep
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p. 4151 - 4158
(2016/07/06)
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- Iron(III) catalyzed halo-functionalization of alkynes
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Abstract Aromatic and aliphatic alkynes can be halo-functionalized to α,α-dihalodimethyl ketals catalyzed by FeCl3 in excellent yields. MeOH is used as a nucleophilic solvent and N-halosuccinimide as the halogen source for this efficient transformation. The resulting α,α-dibromodimethyl ketals can be converted to the corresponding α,α-dibromoketones by treatment with 8% FeCl3 in silica gel.
- Catano, Bryant,Lee, John,Kim, Claudia,Farrell, David,Petersen, Jeffrey L.,Xing, Yalan
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supporting information
p. 4124 - 4127
(2015/08/03)
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- Silica gel catalyzed α-bromination of ketones using N-bromosuccinimide: An easy and rapid method
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An easy and rapid method for the α-bromination of ketones using N-bromosuccinimide (NBS) catalyzed by silica gel in methanol under reflux conditions was developed. The expected products were formed in excellent isolated yields within a short period of time (5-20 min). Major advantages of the present procedure include use of inexpensive and readily available catalyst, exclusion of pre- and post-chemical treatment of catalyst and use of methanol as solvent instead of ethers and chlorinated solvents.
- Mohan Reddy, Bodireddy,Venkata Ramana Kumar, Velpula,Chinna Gangi Reddy, Nallagondu,Mahender Rao, Siripragada
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p. 179 - 182
(2014/02/14)
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- Brominations with Pr4NBr9 as a solid reagent with high reactivity and selectivity
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Tetrapropylammonium nonabromide (Pr4NBr9) is introduced as a room-temperature solid reagent for rapid bromination reactions of various substrates. The reagent exhibits reactivity similar to that of elemental bromine, but shows higher selectivity and it is easier and safer to store and to handle. Georg Thieme Verlag Stuttgart · New York.
- Beck, Thorsten M.,Haller, Heike,Streuff, Jan,Riedel, Sebastian
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p. 740 - 747
(2014/04/03)
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- Steric vs. electronic effects in the Lactobacillus brevis ADH-catalyzed bioreduction of ketones
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Lactobacillus brevis ADH (LBADH) is an alcohol dehydrogenase that is commonly employed to reduce alkyl or aryl ketones usually bearing a methyl, an ethyl or a chloromethyl as a small ketone substituent to the corresponding (R)-alcohols. Herein we have tested a series of 24 acetophenone derivatives differing in their size and electronic properties for their reduction employing LBADH. After plotting the relative activity against the measured substrate volumes we observed that apart from the substrate size other effects must be responsible for the activity obtained. Compared to acetophenone (100% relative activity), other small substrates such as propiophenone, α,α, α-trifluoroacetophenone, α-hydroxyacetophenone, and benzoylacetonitrile had relative activities lower than 30%, while medium-sized ketones such as α-bromo-, α,α-dichloro-, and α,α-dibromoacetophenone presented relative activities between 70% and 550%. Moreover, the comparison between the enzymatic activity and the obtained final conversions using an excess or just 2.5 equiv. of the hydrogen donor 2-propanol, denoted again deviations between them. These data supported that these hydrogen transfer (HT) transformations are mainly thermodynamically controlled. For instance, bulky α-halogenated derivatives could be quantitatively reduced by LBADH even employing 2.5 equiv. of 2-propanol independently of their kinetic values. Finally, we found good correlations between the IR absorption band of the carbonyl groups and the degrees of conversion obtained in these HT processes, making this simple method a convenient tool to predict the success of these transformations. The Royal Society of Chemistry.
- Rodriguez, Cristina,Borzecka, Wioleta,Sattler, Johann H.,Kroutil, Wolfgang,Lavandera, Ivan,Gotor, Vicente
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supporting information
p. 673 - 681
(2014/01/06)
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- Expanding the scope of alcohol dehydrogenases towards bulkier substrates: Stereo- and enantiopreference for α,α-dihalogenated ketones
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Alcohol dehydrogenases (ADHs) were identified as suitable enzymes for the reduction of the corresponding α,α-dihalogenated ketones, obtaining optically pure β,β-dichloro- or β,β-dibromohydrins with excellent conversions and enantiomeric excess. Among the different biocatalysts tested, ADHs from Rhodococcus ruber (ADH-A), Ralstonia sp. (RasADH), Lactobacillus brevis (LBADH), and PR2ADH proved to be the most efficient ones in terms of activity and stereoselectivity. In a further study, two racemic α-substituted ketones, namely α-bromo- α-chloro- and α-chloro-α-fluoroacetophenone were investigated to obtain one of the four possible diastereoisomers through a dynamic kinetic process. In the case of the brominated derivative, only the (1R)-enantiomer was obtained by using ADH-A, although with moderate diastereomeric excess (>99 % ee, 63 % de), whereas the fluorinated ketone exhibited a lower stereoselectivity (up to 45 % de). Bulking up: A series of β,β-dihalohydrins are obtained through alcohol dehydrogenase (ADH) catalyzed bioreduction of the synthesized α,α-dihalogenated ketones. Two racemic acetophenone derivatives are also subjected to this protocol to obtain stereoenriched alcohols through dynamic kinetic resolution (DKR).
- Kedziora, Kinga,Bisogno, Fabricio R.,Lavandera, Ivan,Gotor-Fernandez, Vicente,Montejo-Bernardo, Jose,Garcia-Granda, Santiago,Kroutil, Wolfgang,Gotor, Vicente
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p. 1066 - 1072
(2014/05/06)
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- K 2S 2O 8-mediated difunctionalization of C≡C bonds in water: A simple and efficient approach to α, α -dihaloacetophenones from phenylacetylenes and NaX
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A novel K2S2O8-mediated oxy-1,1-dihalogenation of alkynes with NaX in the presence of water has been developed, affording α,α-dihaloacetophenones in moderate to good yields. The advantages of this reaction are mild reaction conditions, operational simplicity, and use of pure water as reaction medium. A plausible reaction mechanism is proposed on the basis of mechanistic studies.
- Wang, Jing-Yu,Jiang, Qing,Guo, Can-Cheng
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supporting information
p. 3130 - 3138
(2015/10/12)
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- Regioselective α-bromination of aralkyl ketones using n-bromosuccinimide in the presence of montmorillonite K-10 clay: A simple and efficient method
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A simple and more convenient method has been developed for regioselective α-bromination of various aralkyl ketones with N-bromosuccinimide (NBS) in the presence of Montmorillonite K-10 catalyst in methanol at 60-65 °C. The present procedure offers advantages of short reaction time, simple workup, good yields of products and reusability of the catalyst for four times without loss of activity. Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications to view the free supplemental file.
- Mohan, Reddy Bodireddy,Reddy, N. C. Gangi
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p. 2603 - 2614
(2013/07/26)
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