- H2O2-mediated room temperature synthesis of 2-arylacetophenones from arylhydrazines and vinyl azides in water
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An environmentally benign, cost-efficient and practical methodology for the room temperature synthesis of 2-arylacetophenones in water has been discovered. The facile and efficient transformation involves the oxidative radical addition of arylhydrazines with α-aryl vinyl azides in the presence of H2O2 (as a radical initiator) and PEG-800 (as a phase-transfer catalyst). From the viewpoint of green chemistry and organic synthesis, the present protocol is of great significance because of using cheap, non-toxic and readily available starting materials and reagents as well as amenability to gram-scale synthesis, which provides an attractive strategy to access 2-arylacetophenones.
- Luo, Mengqiang,Zhang, Yaohong,Fang, Ping,Li, Yan,Qi, Chenze,Li, Yong,Shen, Runpu,Cheng, Kai,Wang, Hai
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supporting information
p. 630 - 635
(2022/02/01)
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- Regioselection in the synthesis of 4-benzyltetral-1-ones and the new 4-arylbenzosuber-1-ones
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The intramolecular Friedel-Crafts acylation of 4,5-diarylpentanoic acids has the possibility to cyclise to either a 6-membered ring to give 4-benzyltetral-1-one or a 7-membered ring to give 4-arylbenzosuber-1-one. Of these, only the former compound class has previously been reported. The impact of the substituents positioning on the outcome of the cyclisation has been investigated. The complete formation of either the tetralone or the benzosuberone regioisomer was possible under the same reaction conditions, dependent upon the ring activation and/or deactivation of the chosen substituents. Selected bromo or methoxy substituents could be used as auxiliaries, included in precursors to afford the desired regioisomer and then subsequently removed.
- Truong, Daniel,Howard, Brittany L.,Thompson, Philip E.
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- Palladium-catalyzed synthesis of α-aryl acetophenones from styryl ethers and aryl diazonium saltsviaregioselective Heck arylation at room temperature
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Preparation of α-aryl acetophenones from styryl ethers and aryldiazonium salts is described. The reaction is catalyzed by palladium acetate at room temperature in the absence of ligand and base. The developed method is highly attractive in terms of reaction conditions, substrate scope, functional group tolerance and yields. Synthetic applications of the present method are demonstrated by preparing α-aryl indoles and 3-aryl isocoumarin from styryl ethers.
- Kandasamy, Jeyakumar,Lee, Yong Rok,Singh, Adesh Kumar,Venkatesh, Rapelly
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supporting information
p. 7832 - 7837
(2021/09/28)
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- Ruthenium(II)-Catalyzed Cross-Coupling of Benzoyl Formic Acids with Toluenes: Synthesis of 2-Phenylacetophenones
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Herein, we report a direct method to synthesize 2-phenylacetophenone through a ruthenium(II)-catalyzed cross-coupling reaction between acyl and benzyl radical. The various derivatives of 2-phenylacetophenone were prepared easily in moderate to good yields. These reactions provide a straightforward pathway to synthesize a variety of ketones bearing various functional groups.
- Chen, Yujie,Dai, Chenyang,Huang, Zhibin,Jiang, Yaqiqi,Shu, Sai,Yang, Shan,Zhao, Yingsheng
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p. 2955 - 2961
(2021/07/22)
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- Versatile and base-free copper-catalyzed α-arylations of aromatic ketones using diaryliodonium salts
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A ligand and base-free copper catalyzed synthetic method for the efficient α-arylation of aromatic ketones is described. In order to avoid strong bases, ketone-derived silyl enol ethers were employed. Their reaction with diaryliodonium salts as aryl source provided the intermolecular C–C coupling displaying good functional group tolerance and requiring low catalyst loading.
- Bouquin, Maxime,Jaroschik, Florian,Taillefer, Marc
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- Copper-Catalyzed Three-Component Carboboronation of Allenes Using Highly Strained Cyclic Ketimines as Electrophiles
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A diastereoselective copper and NHC-ligand-catalyzed three-component difunctionalization of allenes with bis(pinacolato)diboron and 2H-azirines to afford borylated allylaziridines is described. The reaction exhibits complete diastereoselectivity and good yields, and the further chlorination of the corresponding borylated products was also performed. It is believed that the high ring-strain force of 2H-azirines facilitates the reaction. More chemical transformations of borylated allylaziridines are also reported.
- Deng, Hao,Dong, Yujie,Shangguan, Yu,Yang, Fazhou,Han, Sheng,Wu, Jiaqi,Liang, Bo,Guo, Hongchao,Zhang, Cheng
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supporting information
p. 4431 - 4435
(2021/05/26)
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- The organocatalytic enantiodivergent fluorination of β-ketodiaryl-phosphine oxides for the construction of carbon-fluorine quaternary stereocenters
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Commercially available cinchona alkaloids that can catalyze the enantiodivergent fluorination of β-ketodiarylphosphine oxides were developed to construct carbon-fluorine quaternary stereocenters. This protocol features a wide scope of substrates and excellent enantioselectivities, and it is scalable.
- Xie, Shaolei,He, Zhi-Juan,Zhang, Ling-Hui,Huang, Bo-Lun,Chen, Xiao-Wei,Zhan, Zong-Song,Zhang, Fu-Min
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p. 2069 - 2072
(2021/03/01)
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- Iron-Catalyzed Enantioselective Radical Carboazidation and Diazidation of α,β-Unsaturated Carbonyl Compounds
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Azidation of alkenes is an efficient protocol to synthesize organic azides which are important structural motifs in organic synthesis. Enantioselective radical azidation, as a useful strategy to install a C-N3 bond, remains challenging due to the inherently instability and unique structure of radicals. Here, we disclose an efficient enantioselective radical carboazidation and diazidation of α,β-unsaturated ketones and amides catalyzed by chiral N,N′-dioxide/Fe(OTf)2 complexes. An array of substituted alkenes was transformed to the corresponding α-azido carbonyl derivatives in good to excellent enantioselectivities, benefiting the preparation of chiral α-amino ketones, vicinal amino alcohols, and vicinal diamines. Control experiments and mechanistic studies proved the radical pathway in the reaction process. The DFT calculations showed that the azido transferred to the radical intermediate via an intramolecular five-membered transition state with the internal nitrogen of the Fe-N3 species.
- Dong, Shunxi,Feng, Xiaoming,He, Jun,Liu, Wen,Liu, Xiaohua,Pu, Maoping,Wu, Yun-Dong,Zhang, Tinghui
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p. 11856 - 11863
(2021/08/16)
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- Thianthrenation-enabled α-arylation of carbonyl compounds with arenes
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The Pd-catalyzed α-arylation of carbonyl compounds with simple arenes enabled by site-selective thianthrenation has been demonstrated. This onepot process using thianthrenium salts as the traceless arylating reagents features mild conditions and a broad substrate scope. In addition, this protocol could also tolerate the heterocyclic carbonyl compounds and complex bioactive molecules, which is appealing for medicinal chemistry.
- Huang, Yu-Hao,Nie, Xiao-Xue,Wang, Peng
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supporting information
p. 7716 - 7720
(2020/11/02)
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- Blue Light Promoted Difluoroalkylation of Aryl Ketones: Synthesis of Quaternary Alkyl Difluorides and Tetrasubstituted Monofluoroalkenes
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A facile and cost-effective method for the preparation of fluoroalkylated compounds has been described by the direct photoexcitation of halofluoroalkanes with blue light absorptivity, enabling the difluoroalkylation of aryl ketones. The methodology has provided an efficient, mild, and catalyst-free synthetic method for quaternary difluoroalkylated arenes and tetrasubstituted monofluoroalkenes.
- Li, Kangkui,Chen, Jingchao,Yang, Chunhui,Zhang, Keyang,Pan, Chunxiang,Fan, Baomin,Fan, Baomin
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supporting information
p. 4261 - 4265
(2020/06/04)
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- Two-Step One-Pot Synthesis of Unsymmetrical (Hetero)Aryl 1,2-Diketones by Addition-Oxygenation of Potassium Aryltrifluoroborates to (Hetero)Arylacetonitriles
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An efficient one-pot two-step procedure for the synthesis of unsymmetrical (hetero)aryl 1,2-diketones has been developed. The reaction proceeds through a palladium-catalyzed nucleophilic addition of potassium aryltrifluoroborates to aliphatic nitriles followed by a copper-catalyzed aerobic benzylic C–H oxygenation using molecular oxygen as a green oxidant. This represents the first example of the direct synthesis of unsymmetrical diaryl 1,2-diketones from arylacetonitriles. This method utilizes inexpensive, stable, nontoxic, and readily available starting materials, is highly effective in the presence of both electron-rich and electron-poor nitriles and aryltrifluoroborates, and tolerates a wide variety of functional groups. The synthetic utility of this transformation was shown by increasing the scale of the reaction and by carrying out the one-pot protocol for the preparation of quinoxaline and benzimidazole derivatives. A plausible reaction mechanism has also been proposed.
- Kumar, Yogesh,Jaiswal, Yogesh,Kumar, Amit
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p. 494 - 505
(2018/02/09)
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- From Tetraphenylfurans to Ring-Opened (Z)-1,4-Enediones: ACQ Fluorophores versus AIEgens with Distinct Responses to Mechanical Force and Light
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Two aryl-substituted tetraphenylfurans (TPF-1 and TPF-2) and the corresponding ring-opened (Z)-1,4-enedione derivatives (TPBD-1 and TPBD-2) have been successfully synthesized. Although all the molecules adopt propeller-like configurations, experimental re
- Liu, Xia,Li, Mengwei,Liu, Meifang,Yang, Qiuhua,Chen, Yulan
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p. 13197 - 13204
(2018/09/10)
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- ORGANIC COMPOUND AND ELECTRONIC DEVICE COMPRISING AN ORGANIC LAYER COMPRISING THE ORGANIC COMPOUND
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Organic compounds suitable for organic layers of electronic devices that show reduced driving voltage, increased luminous efficiency and/or increased power efficiency.
- -
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Page/Page column 15; 16
(2018/04/17)
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- ORGANIC COMPOUNDS AND ELECTRONIC DEVICE COMPRISING ORGANIC LAYER COMPRISING ORGANIC COMPOUNDS
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Provided are organic compounds suitable for organic layers of electronic devices that show reduced driving voltage, increased luminous efficiency and/or increased power efficiency.
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- Copper-catalyzed base-accelerated direct oxidation of C-H bond to synthesize benzils, isatins, and quinoxalines with molecular oxygen as terminal oxidant
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We describe herein an efficient and general copper (II)-catalyzed base-accelerated oxidation of the C-H bond to synthesize benzils and isatins. With similar oxidation system an efficient one-pot procedure for the synthesis of quinoxaline derivatives was realized. The two protocols feature using molecular oxygen as terminal oxidant, low catalyst loading, wide substrate scope, and high functional-group tolerance.
- Yu, Jing-Wen,Mao, Shuai,Wang, Yong-Qiang
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p. 1575 - 1580
(2015/03/14)
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- NOVEL DIHYDROPYRIMIDIN-2(1H)-ONE COMPOUNDS AS S-NITROSOGLUTATHIONE REDUCTASE INHIBITORS
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The present invention is directed to novel dihydropyrimidin-2(1H)-one compounds useful as S-nitrosoglutathione reductase (GSNOR) inhibitors, pharmaceutical compositions comprising such compounds, and methods of making and using the same.
- -
-
Page/Page column 138
(2011/04/24)
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- Deoxybenzoins from Stille carbonylative cross-couplings using molybdenum hexacarbonyl
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Stille-type carbonylative cross-couplings, employing palladium catalysis and Mo(CO)6 as the carbon monoxide carrier, were used for the preparation of deoxybenzoins. Straightforward transformations were conveniently performed in closed vessels at 100 °C, providing the products in good yields. Benzyl bromides and chlorides were used as coupling partners with aryl and heteroaryl stannanes. This mild three-component carbonylation employs the destabilizing agent DBU to promote smooth release of carbon monoxide from Mo(CO)6, which made this protocol operationally simple and minimized the formation of Stille diarylmethane products.
- S?vmarker, Jonas,Lindh, Jonas,Nilsson, Peter
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supporting information; experimental part
p. 6886 - 6889
(2011/03/17)
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- Bronsted base-catalyzed one-pot three-component Biginelli-type reaction: An efficient synthesis of 4,5,6-triaryl-3,4-dihydropyrimidin-2(1H)-one and mechanistic study
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(Chemical Equation Presented) An efficient one-pot synthesis of 4,5,6-triaryl-3,4-dihydropyrimidin-2(1H)-ones via a three-component Biginelli-type condensation of aldehyde, 2-phenylacetophenone, and urea/thiourea in the presence of a catalytic amount of t-BuOK (20 mol %) is described. The reactions proceeded efficiently at 70 °C to afford the desired products in moderate to good yields. Detailed mechanistic study shows that the Biginelli-type reaction using urea and thiourea proceeds through two totally different pathways. Enone 5 and bis-urea 8 were highly suggested as respective reaction intermediates for reactions involving thiourea and urea as substrates.
- Shen, Zhi-Liang,Xu, Xiao-Ping,Ji, Shun-Jun
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supporting information; experimental part
p. 1162 - 1167
(2010/04/02)
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- The chemistry of α,β-ditosyloxyketones: Novel routes for the synthesis of desoxybenzoins and α-aryl-β-ketoaldehyde dimethylacetals from α,β-chalcone ditosylates
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The reaction of α,β-chalcone ditosylates 3 with potassium hydroxide in suitable conditions leads to 1,2-aryl shift and carbon-carbon bond cleavage, thereby providing a novel route for the synthesis of 1,2-diarylethan-1-ones 4 and 1,2-diaryl-3,3-dimethoxy propan-1-ones 5. Georg Thieme Verlag Stuttgart.
- Prakash, Om,Kumar, Rajesh,Sharma, Deepak,Pannu, Kamaljeet,Kamal, Raj
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p. 2189 - 2192
(2008/02/10)
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- Peripheral aryl-substituted pyrrole fluorophores for glassy blue-light-emitting diodes
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In this work, a series of aryl-substituted pyrrole analogues were synthesized. These pyrrole analogues emit violet to blue light. Fluorescence and amorphous glassy properties of these pyrrole analogues were induced by manipulating the peripheral aryl grou
- Kuo, Wen-Jang,Chen, Ying-Hsiao,Jeng, Ru-Jong,Chan, Li-Hsin,Lin, Wen-Peng,Yang, Zhe-Ming
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p. 7086 - 7096
(2008/02/09)
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- Catalytic cross-coupling reaction of esters with organoboron compounds and decarbonylative reduction of esters with HCOONH4: A new route to acyl transition metal complexes through the cleavage of acyl-oxygen bonds in esters
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The Ru3(CO)12-catalyed cross-coupling reaction of esters with organoboron compounds leading to ketones is described. A wide variety of functional groups can be tolerated under the reaction conditions. Aromatic boronates function as a coupling partner to give aryl ketones. Acyl-alkyl coupling to dialkyl ketones is also achieved by the use of 9-alkyl-9-BBN in place of boronates. The Ru3(CO)12- catalyzed decarbonylative reduction of esters with ammonium formate (HCOONH 4) leading to hydrocarbons is also described. No expected aldehydes are produced, and controlled experiments indicate that aldehydes are not intermediate for the transformation. A hydrosilane can also be used as a reducing reagent in place of HCOONH4. A wide variety of functional groups are compatible for both reactions. The key step for both catalytic reactions is the directing group-promoted cleavage of an acyl carbon-oxygen bond in esters, leading to the generation of acyl transition metal alkoxo complexes.
- Tatamidani, Hiroto,Yokota, Kazuhiko,Kakiuchi, Fumitoshi,Chatani, Naoto
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p. 5615 - 5621
(2007/10/03)
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- Nucleophilic benzoylation using a mandelic acid dioxolanone as a synthetic equivalent of the benzoyl carbanion. Oxidative decarboxylation of α-hydroxyacids
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The synthesis of alkyl aryl ketones using a mandelic acid dioxolanone as a synthetic equivalent (Umpolung) of the benzoyl carbanion is reported. The methodology involves alkylation of the mandelic acid dioxolanone, hydrolysis of the dioxolanone moiety in the alkylated products and oxidative decarboxylation of the resulting α-hydroxyacids. The last step is carried out in a catalytic aerobic way using a Co (III) complex in the presence of pivalaldehyde under very mild conditions.
- Blay, Gonzalo,Fernandez, Isabel,Monje, Belen,Pedro, Jose R.
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p. 365 - 372
(2007/10/03)
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- Direct preparation of benzylic manganese reagents from benzyl halides, sulfonates, and phosphates and their reactions: Applications in organic synthesis
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The use of highly active manganese (Mn)*, prepared by the Rieke method, was investigated for the direct preparation of benzylic manganese reagents. The oxidative addition of the highly active manganese to benzylic halides was easily completed under mild conditions. Moreover, benzylic manganese sulfonates and phosphates were prepared by direct oxidative addition of Mn* to the carbon-oxygen bonds of benzylic sulfonates and phosphates. The resulting benzylic manganese reagents were found to undergo cross-coupling reactions with a variety of electrophiles. Most of these reactions were carried out in the absence of any transition metal catalyst under mild conditions. In addition, the use of highly active manganese was also studied for preparation of homo-coupled products of functionalized benzyl halides without transition metal catalysts. These useful approaches provided not only a facile synthetic route to the preparation of resoricinolic lipids but a facile synthesis of functionalized 4-benzylpyridines by regioselective and chemo selective γ-addition of benzylic group to N-alkoxycarbonylpyridinum salts.
- Suh, YoungSung,Lee, Jun-Sik,Kim, Seoung-Hoi,Rieke, Reuben D.
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- Polyphenylene oligomers and polymers
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The present invention refers to aromatic monomers containing at least one cyclopentadienone moiety and at least one acetylene moiety and oligomers, uncured polymers and cured polymers comprising the reaction product thereof.
- -
-
Example 1A(b)
(2008/06/13)
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- Benzylic Manganese Halides, Sulfonates, and Phosphates: Preparation, Coupling Reactions, and Applications in Organic Synthesis
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The use of highly active manganese, prepared by the Rieke method, for the direct preparation of benzylic manganese reagents was investigated. The oxidative addition of the highly active manganese (Mn*) to benzylic halides was easily completed under mild conditions. More importantly, benzylic manganese sulfonates and phosphates were prepared by direct oxidative addition of Mn* to the carbon-oxygen bonds of benzylic sulfonates and phosphates. The resulting benzylic manganese reagents were found to undergo cross-coupling reactions with a variety of electrophiles. The majority of these reactions were carried out in the absence of any transition metal catalyst under mild conditions. This approach also provided a facile synthetic route to the preparation of resorcinolic lipids.
- Kim, Seung-Hoi,Rieke, Reuben D.
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p. 2322 - 2330
(2007/10/03)
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- A new synthetic protocol for the direct preparation of organomanganese reagents; organomanganese tosylates and mesylates
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A new synthetic route to organomanganese sulfonate reagents has been developed. These useful reagents can be readily prepared via direct oxidative addition of highly reactive manganese to carbon-oxygen bonds of the corresponding tosylates and mesylates under mild conditions.
- Kim, Seung-Hoi,Rieke, Reuben D.
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p. 4931 - 4934
(2007/10/03)
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- The reaction of active zinc with organic bromides
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The oxidative addition of highly reactive zinc to organic bromides shows a pronounced structure-reactivity dependence, in contrast to that shown by other metals. The kinetic and LFER studies suggest a mechanism in which electron transfer (ET) is the rate-determining step of the reaction. Experiments carried out with radical clocks as well as the stereochemical outcome of the reaction support the presence of radicals. The reactivity profiles suggest that the ET has an important component of inner-sphere process in the reaction with alkyl bromides. In the case of aryl halides, Hammet plots are consistent with the participation of aryl halide radical anions as intermediates. The reaction contemplated here can be ascribed as another example of radical-mediated selective reaction, and it has straightforward synthetic applications. Some synthetic work was done in this direction, to demonstrate how this structure-reactivity dependence can be used to obtain selective organozinc formation in unsymmetrical dibromides.
- Guijarro, Albert,Rosenberg, David M.,Rieke, Reuben D.
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p. 4155 - 4167
(2007/10/03)
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- 10,5-(Iminomethano)-10,11-dihydro-5H-dibenzo[a,d]cycloheptene and derivatives. Potent PCP receptor ligands
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IDDC (3, 10,5-(iminomethano)-10,11-dihydro-5H-dibenzo[a,d]cycloheptene) and a series of substituted derivatives were synthesized and evaluated in vitro for their ability to displace tritiated MK-801 ([3H]-2) from its specific binding site in guinea pig brain homogenate. Substitution at the 3- position of 3 with bromine, chlorine, and fluorine led to increased binding affinity. In contrast, substitution of donor groups at the 3-position gave decreased binding affinities, as did all substitutions at the 7-position and on nitrogen. Where racemic mixtures were resolved, the (+)-optical antipodes were more active than their enantiomers or racemates. The most active ligand found in this study was (+)-13e (IC50 = 15.5 ± 4.5 nM). The affinity of (+)-13e for the PCP receptor makes it among the most potent ligands known. In vitro neuroprotection was demonstrated by 3, (+)-3, and (+)-6 (N-Me-IDDC) against glutamate-induced cell death in rat hippocampal cells.
- Gee,Barmettler,Rhodes,McBurney,Reddy,Hu -,Cotter,Hamilton,Weber,Keana
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p. 1938 - 1946
(2007/10/02)
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- Metallic Nickel-Mediated Synthesis of Ketones by the Reaction of Benzylic, Allylic, Vinylic, and Pentafluorophenyl Halides with Acid Halides
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Metallic nickel was investigated as a convenient coupling reagent for the synthesis of ketones by the reaction of benzylic, allylic, vinylic, and pentafluorophenyl halides with acid halides at 85 deg C in glyme.A variety of benzylic ketones with functional groups including halogen, cyano, methoxycarbonyl, and hydroxycarbonyl groups were prepared in good yields by this method.The reaction was demonstrated to proceed via organonickel halide intermediates formed by the smooth oxidative addition of benzylic and acyl halides to metallic nickel, which were trapped with electron-deficient olefins. (?-Allyl)nickel halides, prepared in situ at 85 deg C from allylic halides and the nickel, also worked for the preparation of ketones.Vinylic and pentafluorophenyl halides but not alkyl halides reacted with acid halides to give the corresponding ketones in moderate yields.
- Inaba, Shin-ichi,Rieke, Reuben D.
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p. 1373 - 1381
(2007/10/02)
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- ARYL REARRANGEMENT ON THE PHOTOLYSIS OF 2-ARYL-2-ETHOXY-2-PHENYLETHYL CABALOXIME.
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The photolysis of 2-aryl-2-ethoxy-2-phenylethyl cobaloxime followed by hydrolysis gave two kinds of substituted 1,2-diphenylethanones arising via phenyl or substituted-phenyl migration. The substituent effect on the aryl rearrangement is similar to that on the reported neophyl rearrangement, and the rearrangement takes place by a radical mechanism without the deep involvement of cobaloxine(II).
- Tada,Inoue,Okabe
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p. 1420 - 1423
(2007/10/02)
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