- Copper-Catalyzed Radical 1,2-Carbotrifluoromethylselenolation of Alkenes under Ambient Conditions
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We have described a copper-catalyzed radical 1,2-carbotrifluoromethylselenolation of alkenes using the readily available alkyl halides and (Me4N)SeCF3 salt. Critical to the success is the use of a proline-based N,N,P-ligand to enhance the reducing capabil
- Yu, Jiao,Yang, Ning-Yuan,Cheng, Jiang-Tao,Zhan, Tian-Ya,Luan, Cheng,Ye, Liu,Gu, Qiang-Shuai,Li, Zhong-Liang,Chen, Guo-Qiang,Liu, Xin-Yuan
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Read Online
- Nickel-Catalyzed Reductive Cross-Coupling of Aryl Bromides with Vinyl Acetate in Dimethyl Isosorbide as a Sustainable Solvent
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A nickel-catalyzed reductive cross-coupling has been achieved using (hetero)aryl bromides and vinyl acetate as the coupling partners. This mild, applicable method provides a reliable access to a variety of vinyl arenes, heteroarenes, and benzoheterocycles, which should expand the chemical space of precursors to fine chemicals and polymers. Importantly, a sustainable solvent, dimethyl isosorbide, is used, making this protocol more attractive from the point of view of green chemistry.
- Su, Mincong,Huang, Xia,Lei, Chuanhu,Jin, Jian
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supporting information
p. 354 - 358
(2022/01/15)
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- Mur ligases inhibitors with azastilbene scaffold: Expanding the structure–activity relationship
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Antibiotic resistance represents one of the biggest public health challenges in the last few years. Mur ligases (MurC–MurF) are involved in the synthesis of UDP-N-acetylmuramyl-pentapeptide, the main building block of bacterial peptidoglycan polymer. They are essential for the survival of bacteria and therefore important antibacterial targets. We report herein the synthesis and structure–activity relationships of Mur ligases inhibitors with an azastilbene scaffold. Several compounds showed promising inhibitory potencies against multiple ligases and one compound also possessed moderate antibacterial activity. These results represent a solid ground for further development and optimization of structurally novel antimicrobial agents to combat the rising bacterial resistance.
- Hrast, Martina,Frlan, Rok,Knez, Damijan,Zdovc, Irena,Barreteau, Hélène,Gobec, Stanislav
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supporting information
(2021/05/10)
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- A convenient reagent for the conversion of aldoximes into nitriles and isonitriles
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For the dehydroxylation of aldoximes with 4-nitro-1-((trifluoromethyl)sulfonyl)-imidazole (NTSI), slight modifications of reaction conditions resulted in significantly different reaction paths to provide either nitriles or isonitriles. The challenging conversion of aldoximes into isonitriles was achieved under mild conditions.
- Zhang, Wei,Lin, Jin-Hong,Zhang, Pengfei,Xiao, Ji-Chang
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supporting information
p. 6221 - 6224
(2020/06/29)
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- Copper-Catalyzed Asymmetric Radical 1,2-Carboalkynylation of Alkenes with Alkyl Halides and Terminal Alkynes
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A copper-catalyzed intermolecular three-component asymmetric radical 1,2-carboalkynylation of alkenes has been developed, providing straightforward access to diverse chiral alkynes from readily available alkyl halides and terminal alkynes. The utilization of a cinchona alkaloid-derived multidentate N,N,P-ligand is crucial for the efficient radical generation from mildly oxidative precursors by copper and the effective inhibition of the undesired Glaser coupling side reaction. The substrate scope is broad, covering (hetero)aryl-, alkynyl-, and aminocarbonyl-substituted alkenes, (hetero)aryl and alkyl as well as silyl alkynes, and tertiary to primary alkyl radical precursors with excellent functional group compatibility. Facile transformations of the obtained chiral alkynes have also been demonstrated, highlighting the excellent complementarity of this protocol to direct 1,2-dicarbofunctionalization reactions with C(sp2/sp3)-based reagents.
- Dong, Xiao-Yang,Cheng, Jiang-Tao,Zhang, Yu-Feng,Li, Zhong-Liang,Zhan, Tian-Ya,Chen, Ji-Jun,Wang, Fu-Li,Yang, Ning-Yuan,Ye, Liu,Gu, Qiang-Shuai,Liu, Xin-Yuan
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supporting information
p. 9501 - 9509
(2020/05/18)
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- Ni-Catalyzed Reductive Cyanation of Aryl Halides and Phenol Derivatives via Transnitrilation
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Herein, we report a Ni-catalyzed reductive coupling for the synthesis of benzonitriles from aryl (pseudo)halides and an electrophilic cyanating reagent, 2-methyl-2-phenyl malononitrile (MPMN). MPMN is a bench-stable, carbon-bound electrophilic CN reagent that does not release cyanide under the reaction conditions. A variety of medicinally relevant benzonitriles can be made in good yields. Addition of NaBr to the reaction mixture allows for the use of more challenging aryl electrophiles such as aryl chlorides, tosylates, and triflates. Mechanistic investigations suggest that NaBr plays a role in facilitating oxidative addition with these substrates.
- Mills, L. Reginald,Graham, Joshua M.,Patel, Purvish,Rousseaux, Sophie A. L.
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supporting information
p. 19257 - 19262
(2019/12/02)
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- Rhenium-Catalyzed Decarboxylative Tri-/Difluoromethylation of Styrenes with Fluorinated Carboxylic Acid-Derived Hypervalent Iodine Reagents
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Herein, unprecedented rhenium-catalyzed decarboxylative oxytri-/difluoromethylation and Heck-type trifluoromethylation of styrenes have been developed by using hypervalent iodine(III) reagents derived from cheap, stable, and easy-handling fluorinated carboxylic acids. Mechanistic studies revealed a radical decarboxylative trifluoromethylation pathway occurring in these reactions.
- Wang, Yin,Yang, Yunhui,Wang, Congyang
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supporting information
p. 1229 - 1233
(2019/11/21)
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- Enantioselective, Catalytic Vicinal Difluorination of Alkenes
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The enantioselective, catalytic vicinal difluorination of alkenes is reported by II/IIII catalysis using a novel, C2-symmetric resorcinol derivative. Catalyst turnover via in situ generation of an ArIIIIF2 species is enabled by Selectfluor oxidation and addition of an inexpensive HF–amine complex. The HF:amine ratio employed in this process provides a handle for regioselective orthogonality as a function of Br?nsted acidity. Selectivity reversal from the 1,1-difluorination pathway (geminal) to the desired 1,2-difluorination (vicinal) is disclosed (>20:1 in both directions). Validation with electron deficient styrenes facilitates generation of chiral bioisosteres of the venerable CF3 unit that is pervasive in drug discovery (20 examples, up to 94:06 e.r.). An achiral variant of the reaction is also presented using p-TolI (up to >95 % yield).
- Scheidt, Felix,Sch?fer, Michael,Sarie, Jér?me C.,Daniliuc, Constantin G.,Molloy, John J.,Gilmour, Ryan
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supporting information
p. 16431 - 16435
(2018/11/23)
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- Catalytic Geminal Difluorination of Styrenes for the Construction of Fluorine-rich Bioisosteres
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A geminal difluorination of alkenes based on I(I)/I(III) catalysis is disclosed, which is compatible with a range of electronically and substitutionally diverse styrenes (27 examples, up to 89% yield). Employing inexpensive p-TolI as the organocatalyst, turnover is enabled by Selectfluor-mediated oxidation to generate the ArIF2 species in situ. Extension to include α-substituted styrenes bearing fluorine-containing groups is disclosed and provides an expansive platform for the generation of fluorine-rich architectures.
- Scheidt, Felix,Neufeld, Jessica,Sch?fer, Michael,Thiehoff, Christian,Gilmour, Ryan
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supporting information
p. 8073 - 8076
(2019/01/04)
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- NHC-catalyzed hydroacylation of styrenes
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New hydroacylation catalysts: Highly electron-rich N-heterocyclic carbenes (NHCs) facilitate the intermolecular hydroacylation of unstrained olefins. This unprecedented organocatalytic coupling joins simple and abundant aldehydes and styrenes to yield valuable ketone products. EWG=electron-withdrawing group, EDG=electron-donating group. Copyright
- Schedler, Michael,Wang, Duo-Sheng,Glorius, Frank
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supporting information
p. 2585 - 2589
(2013/04/10)
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- Flow Chemistry Syntheses of Styrenes, Unsymmetrical Stilbenes and Branched Aldehydes
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Two tandem flow chemistry processes have been developed. A single palladium-catalysed Heck reaction with ethylene gas provides an efficient synthesis for functionalised styrenes. Through further elaboration the catalyst becomes multi-functional and performs a second Heck reaction providing a single continuous process for the synthesis of unsymmetrical stilbenes. In addition, the continuous, rhodium-catalysed, hydroformylation of styrene derivatives with syngas affords branched aldehydes with good selectivity. Incorporation of an in-line aqueous wash and liquid-liquid separation allowed for the ethylene Heck reaction to be telescoped into the hydroformylation step such that a single flow synthesis of branched aldehydes directly from aryl iodides was achieved. The tube-in-tube semi-permeable membrane-based gas reactor and liquid-liquid separator both play an essential role in enabling these telescoped flow processes.
- Bourne, Samuel L.,O'Brien, Matthew,Kasinathan, Sivarajan,Koos, Peter,Tolstoy, Paeivi,Hu, Dennis X.,Bates, Roderick W.,Martin, Benjamin,Schenkel, Berthold,Ley, Steven V.
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p. 159 - 172
(2013/03/13)
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- The continuous-flow synthesis of styrenes using ethylene in a palladium-catalysed heck cross-coupling reaction
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We report a palladium-catalysed ethylene Heck reaction for the vinylation of aryl iodides using a tube-in-tube gas-liquid reactor. The flow process afforded various styrenes in short reaction times, employing moderate ethylene pressure. Georg Thieme Verlag Stuttgart · New York.
- Bourne, Samuel L.,Koos, Peter,Obrien, Matthew,Martin, Benjamin,Schenkel, Berthold,Baxendale, Ian R.,Ley, Steven V.
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scheme or table
p. 2643 - 2647
(2011/12/04)
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- Low pressure vinylation of aryl and vinyl halides via Heck-Mizoroki reactions using ethylene
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Aryl bromides and iodides in the presence of catalytic amounts of a palladacycle derived from acetophenone oxime and 2 equiv of potassium acetate react with ethylene under ambient pressure (15-30 psi) to give the corresponding vinylarenes. The reactions work with both electron-deficient and electron-rich aryl compounds and tolerate wide variety of common functional groups. Vinyl bromides lead to 1,3-dienes in moderate yields.
- Smith, Craig R.,RajanBabu
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supporting information; experimental part
p. 1102 - 1110
(2010/03/25)
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- METHODS OF TREATING AMYLOIDOSIS USING ARYL-CYCLOPROPYL DERIVATIVE ASPARTYL PROTEASE INHIBITORS
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The invention relates to novel compounds and methods of treating diseases, disorders, and conditions associated with amyloidosis. Amyloidosis refers to a collection of diseases, disorders, and conditions associated with abnormal deposition of A-beta prote
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Page/Page column 94
(2010/11/27)
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- Suzuki-Miyaura cross-coupling reactions of potassium vinyltrifluoroborate with aryl and heteroaryl electrophiles
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We have previously reported that the palladium-catalyzed cross-coupling reaction of potassium vinyltrifluoroborate with aryl electrophiles proceeds with good yields. Herein, we describe recent progress in optimizing the reaction, as well as outlining the scope and limitations of the reaction. The cross-coupling reaction can generally be effected using 2 mol % of PdCl2 and 6 mol % of PPh3 as a catalyst system in THF/H2O with Cs 2CO3 as a base. Moderate to good yields are obtained in the presence of a variety of functional groups.
- Molander, Gary A.,Brown, Adam R.
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p. 9681 - 9686
(2007/10/03)
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- HETEROCYCLIC COMPOUNDS HAVING AN OXADIAZOLE MOIETY AND HYDRO ISOMERS THEREOF
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The present invention relates to substituted diphenyl heterocycle compounds having an oxadiazole moiety and pharmaceuticals compositions thereof that inhibit replication of HCV virus. The present invention also relates to the use of the compounds and/or compositions to inhibit HCV replication and/or proliferation and to treat or prevent HCV infections.
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- Bacterial monooxygenase mediated preparation of nonracemic chiral oxiranes: Study of the effects of substituent nature and position
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Monooxygenation of styrene derivatives using recombinant E. coli biocatalyst is an efficient way to prepare the corresponding oxiranes. The electronic and geometric effects of the ring substituents are described and show the relaxed specificity of the enzyme and its high stereoselectivity.
- Bernasconi, Silvana,Orsini, Fulvia,Sello, Guido,Di Gennaro, Patrizia
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p. 1603 - 1606
(2007/10/03)
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- Factor xa inhibitors with aryl-amidines and derivatives, and prodrugs thereof
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The present invention relates to a compound with aryl-amidines, particularly amidinoaryl-cyclopropanes, amidinoarylmethyl-pyrroles, amidinoaryl-benzenes, amidinoaryl-pyridines, or amindonoaryl-alanines, represented by formula (1), a pharmaceutically acceptable salt, a prodrug, a hydrate, a solvate or an isomer thereof, which are inhibitors of coagulation enzyme, factor Xa (FXa). The present invention also relates to a pharmaceutical composition containing the compound, and a method of using the same as an anticoagulant agent for treatment and prevention of thrombosis disorders.
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- Synthesis of Substituted 1,4-Divinylbenzenes by Heck Reactions with Compressed Ethene
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Substituted 1,4-divinylbenzenes 3a-i were synthesized by twofold Heck coupling from the corresponding 1,4-dibromo- (electron withdrawing substituents) or 1,4-diiododialkoxybenzenes 1a-i and ethene. Oligomerizations could be suppressed by increasing the pressure of ethene to 30 bar, simultaneously improving the yields of the title compounds.
- Detert, Heiner,Sugiono, Erli
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p. 358 - 362
(2007/10/03)
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