- Diastereoselective intramolecular Ritter reaction: generation of a cis-fused hexahydro-4aH-indeno[1,2-b]pyridine ring system with 4a,9b-diangular substituents.
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Indanol intermediates 5, prepared via Michael addition of 1-indanone beta-ketoester and acrylonitrile followed by reduction or Grignard reaction of the ketone group, were submitted to intramolecular Ritter reaction using various acid reaction conditions t
- Van Emelen,De Wit,Hoornaert,Compernolle
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Read Online
- Incorporation of diarylbutylamine pharmacophore into indeno- or naphtho[1,2-b]pyran ring systems
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Various conformationally constrained forms of the diarylbutylamine pharmacophore were accessed by incorporating it into heterocyclic ring systems, i.e., indeno[1,2-b]furan, indeno[1,2-b]pyran, naphtho[1,2-b]furan, and benzo[h]chromene. These compounds were formed by epoxidation of 2-alkenyl-substituted 1-indanols or 1-naphthalenols. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.
- Maertens, Faye,Toppet, Suzanne,Compernolle, Frans,Hoornaert, Georges J.
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- Enantioselective electrophilic trifluoromethylthiolation of β-ketoesters: A case of reactivity and selectivity bias for organocatalysis
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A chiral Lewis base or a phase-transfer catalyst (PTC) can mediate the highly enantioselective trifluoromethylthiolation of β-ketoesters with the previously developed SCF3 reagent (see scheme). Reactions of indanone-derived β-ketoesters occurre
- Wang, Xueqiang,Yang, Tao,Cheng, Xiaolin,Shen, Qilong
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- Synthesis of cis-fused hexahydro-4aH-indeno[1,2-b]pyridines via intramolecular Ritter reaction and their conversion into tricyclic analogues of NK-1 and dopamine receptor ligands
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Indanol intermediates prepared via Michael addition of 1-indanone β-ketoester and acrylonitrile, followed by Grignard reaction of the ketone group, were submitted to an intramolecular Ritter reaction to produce cis-fused methyl 2-oxo-9b-phenyl-1,2,3,4,5,9b-hexahydro-4aH-indeno[1,2-b]pyridine-4a- carboxylates with 4a,9b-diangular substitution pattern. Further transformation of the bridgehead ester group and the lactam function afforded constrained tricyclic analogues of some monocyclic piperidine NK-1 antagonists and of a bicyclic dopamine receptor ligand.
- Emelen, Kristof Van,De Wit, Tom,Hoornaert, Georges J,Compernolle, Frans
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- Photo-organocatalytic enantioselective perfluoroalkylation of β-ketoesters
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The visible-light-driven, phase-transfer-catalyzed, enantioselective perfluoroalkylation and trifluoromethylation of cyclic β-ketoesters is described. The photo-organocatalytic process, which occurs at ambient temperature and under visible light illumination, is triggered by the photochemical activity of in situ-generated electron donor-acceptor complexes, arising from the association of chiral enolates and perfluoroalkyl iodides. Preliminary mechanistic studies are reported.
- Wo?niak, ?ukasz,Murphy, John J.,Melchiorre, Paolo
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- Catalytic asymmetric fluorination of Alkyl 1-indanone-2-carboxylates Ruled by Pybox-Eu(III) Combination
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A highly enantioselective catalytic method for the synthesis of quaternary α-fluoro derivatives of 3-oxo esters is described. The reaction uses europium (III) triflate and commercially available chiral pybox-type C2-symmetric ligand. Excellent results in
- Granados, Albert,Sarró, Pau,Vallribera, Adelina
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Read Online
- Electrochemical α-thiolation and azidation of 1,3-dicarbonyls
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A highly efficient electrochemical α-thiolation and azidation of 1,3-dicarbonyl compounds is developed. This electrochemical process is conducted under mild conditions without the use of a chemical oxidant, and exhibits a wide scope with good functional g
- Guo, Yonghong,He, Chuan,Ke, Jie,Zhu, Liru,Zu, Bing
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supporting information
p. 2758 - 2761
(2022/03/07)
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- Hypervalent Iodine(III) Reagents with Transferable Primary Amines: Structure and Reactivity on the Electrophilic α-Amination of Stabilized Enolates
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A new family of hypervalent iodine reagents containing transferable primary amine groups is described. Benziodoxolone-based reagents were synthesized on the gram-scale through operationally simple reactions in up to quantitative yields. These bench-stable solids were characterized by X-ray analysis and successfully employed in the α-amination of indanone-based β-ketoesters in up to 83% yield. Mechanistic studies indicate a substitution mechanism involving an electrophilic amine.
- Poeira, Diogo L.,Negr?o, Ana Cláudia R.,Faustino, Hélio,Coelho, Jaime A. S.,Gomes, Clara S. B.,Gois, Pedro M. P.,Marques, M. Manuel B.
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supporting information
p. 776 - 781
(2022/01/20)
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- Tosyloxybenziodoxolone: A Platform for Performing the Umpolung of Alkynes in One-Pot Transformations
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Ethynylbenziodoxolones (EBXs) are commonly encountered reagents for the electrophilic alkynylation of nucleophiles. Herein, we report a one-pot, two-step process for EBX generation and their direct application in substrate functionalization. Our approach enables us to bypass the originally mandatory isolation and purification of the reagents, resulting in a more efficient synthesis. We could apply this process to seven different transformations involving both two- and one-electron nucleophiles to obtain a large variety of alkynylated products.
- Borrel, Julien,Waser, Jerome
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supporting information
p. 142 - 146
(2021/12/27)
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- METHOD FOR PREPARING 1,3-DICARBONYL COMPOUND BASED ON METAL HYDRIDE/PALLADIUM COMPOUND SYSTEM
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Disclosed is a method for preparing a 1,3-dicarbonyl compound based on a metal hydride/palladium compound system. The method includes the following steps: suspending a palladium compound and a metal hydride in a solvent under the protection of nitrogen, t
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Paragraph 0023-0024
(2021/07/10)
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- APPLICATION OF METAL HYDRIDE/PALLADIUM COMPOUND SYSTEM IN PREPARATION OF 1,3-DICARBONYL COMPOUND IN CASCADE REACTION OF ELECTRON-DEFICIENT ALKENE COMPOUND
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Provided is an application of a metal hydride/palladium compound system in the preparation of a 1,3-dicarbonyl compound in a cascade reaction of an electron-deficient alkene compound, said reaction comprising the following steps: under the protection of n
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Paragraph 0023-0038
(2021/07/10)
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- Intermediate compound of immunomodulator
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The present invention relates to an intermediate compound of an IL-17A immunomodulator compound. The IL17A immunomodulator compound synthesized by the intermediate compound provided by the invention has good IL-17A inhibition activity.
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Paragraph 0124-0128
(2021/02/10)
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- Synthesis of Diverse Aryliodine(III) Reagents by Anodic Oxidation?
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An anodic oxidation enabled synthesis of hypervalent iodine(III) reagents from aryl iodides is demonstrated. Under mild electrochemical conditions, a range of aryliodine(III) reagents including iodosylarenes, (difunctionaliodo)arenes, benziodoxoles and diaryliodonium salts can be efficiently synthesized and derivatized in good to excellent yields with high selectivity. As only electrons serve as the oxidation reagents, this method offers a more straightforward and sustainable manner avoiding the use of expensive or hazardous chemical oxidants.
- Zu, Bing,Ke, Jie,Guo, Yonghong,He, Chuan
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supporting information
p. 627 - 632
(2021/02/12)
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- Convincing Catalytic Performance of Oxo-Tethered Ruthenium Complexes for Asymmetric Transfer Hydrogenation of Cyclic α-Halogenated Ketones through Dynamic Kinetic Resolution
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A highly efficient dynamic kinetic resolution of cyclic halohydrins was achieved by the asymmetric transfer hydrogenation of racemic α-haloketones. Bifunctional oxo-tethered Ru(II) catalysts could promote the reduction without deterioration of halogens. By structural tuning of the catalyst, chiral alcohols having halogen, ester, carboxamide, and sulfone functions were obtained variably with excellent diastereo- and enantioselectivities (up to >99:1 d.r. and >99.9 ee), which provided a concise synthetic approach to a dopamine D3 receptor ligand, (+)-PHNO.
- Touge, Taichiro,Nara, Hideki,Kida, Michio,Matsumura, Kazuhiko,Kayaki, Yoshihito
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supporting information
p. 3070 - 3075
(2021/05/05)
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- Trifluorinated Tetralins via I(I)/I(III)-Catalysed Ring Expansion: Programming Conformation by [CH2CH2] → [CF2CHF] Isosterism
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Saturated, fluorinated carbocycles are emerging as important modules for contemporary drug discovery. To expand the current portfolio, the synthesis of novel trifluorinated tetralins has been achieved. Fluorinated methyleneindanes serve as convenient precursors and undergo efficient difluorinative ring expansion with in situ generated p-TolIF2 (>20 examples, up to >95 %). A range of diverse substituents are tolerated under standard catalysis conditions and this is interrogated by Hammett analysis. X-ray analysis indicates a preference for the CH?F bond to occupy a pseudo-axial orientation, consistent with stabilising σC?H→σC?F* interactions. The replacement of the symmetric [CH2?CH2] motif by [CF2?CHF] removes the conformational degeneracy intrinsic to the parent tetralin scaffold leading to a predictable half-chair. The conformational behavior of this novel structural balance has been investigated by computational analysis and is consistent with stereoelectronic theory.
- Daniliuc, Constantin G.,Gilmour, Ryan,Mück-Lichtenfeld, Christian,Neufeld, Jessica,Stünkel, Timo
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supporting information
p. 13647 - 13651
(2021/05/07)
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- Immunomodulator
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The invention discloses an immunomodulator, and particularly relates to compounds for inhibiting IL-17A and application of the compounds serving as the immunomodulator in preparation of drugs. The invention discloses an application of a compound shown as a formula I or a stereoisomer thereof in preparing medicines for inhibiting IL-17A, and provides a new choice for clinically screening and/or preparing medicines for treating diseases related to IL-17A activity.
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Paragraph 0114-0118
(2021/02/10)
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- Immunomodulator
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The invention discloses an immunomodulator, and particularly relates to a compound shown as a formula I, or a stereoisomer thereof, or a pharmaceutically acceptable salt thereof. Experiments prove that the compound has good IL-17A inhibitory activity, can be used for preparing an IL-17A inhibitor and drugs for preventing and/or treating IL-17A mediated diseases (such as inflammation, autoimmune diseases, infectious diseases, cancers and precancerous syndromes), and provides a new medical possibility for clinical treatment of diseases related to abnormal IL-17A activity.
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Paragraph 0130-0134
(2021/02/10)
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- Highly Selective Difluoromethylations of β-Keto Amides with -TMSCF 2Br under Mild Conditions
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Without employing any transition metal and other additives, efficient methods for selective difluoromethylations of β-keto amides with TMSCF 2 Br reagent have been developed under mild conditions. This protocol allows a convenient access to various α-difluoromethyl β-keto amides with excellent yields (up to 93%) and high carbon/oxygen (C/O) regioselectivities (up to 99:1). The C/O selectivity of β-keto amides could be easily reversed and controlled by simply changing the base. This protocol can be easily scaled-up and the C-difluoromethylation product could be reduced into CF 2 H-containing amino alcohol derivatives. Moreover, the first enantioselective electrophilic difluoromethylation of β-keto amides has been achieved by phase-transfer catalysis.
- Chen, Pengli,Fu, Yang,Hu, Yanqin,Wang, Shuaifei,Wang, Yakun,Zhang, Conghui,Zhang, Mingwei,Zhao, Ting
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supporting information
p. 1123 - 1130
(2021/06/18)
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- Radical-Polar Crossover Annulation: A Platform for Accessing Polycyclic Cyclopropanes
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Photoredox-mediated radical/polar crossover (RPC) processes provide unique solutions to challenging annulations. Herein, we describe an approach to the cyclopropanation of olefins that are embedded within bicyclic scaffolds. Whereas these systems are noto
- Milligan, John A.,Burns, Kevin L.,Le, Anthony V.,Polites, Viktor C.,Wang, Zheng-Jun,Molander, Gary A.,Kelly, Christopher B.
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supporting information
p. 242 - 247
(2019/12/11)
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- Ring-Strain-Enabled Catalytic Asymmetric Umpolung C-O Bond-Forming Reactions of 1,2-Oxazetidines for the Synthesis of Functionalized Chiral Ethers
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An unprecedented catalytic asymmetric umpolung C-O bond-forming reaction of N-nosyl 1,2-oxazetidines with β-keto esters has been achieved in the presence of a chiral phase-transfer catalyst, allowing access to a range of highly functionalized chiral ethers bearing quaternary and no adjacent stereogenic centers with high yields, excellent enantioselectivities, and diastereoselectivities (up to 97percent ee and 20:1 dr). These versatile products could be flexibly transformed into biologically important chiral fused and spiro morpholines in two steps.
- Wu, Binyu,Yang, Jinggang,Gao, Min,Hu, Lin
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supporting information
p. 5561 - 5566
(2020/07/14)
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- Synthesis and antitumor activity of aza-brazilan derivatives containing imidazolium salt pharmacophores
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The synthesis of a series of novel aza-brazilan derivatives containing imidazolium salt pharmacophores is presented. The biological activity of such imidazolium salts was further evaluated in vitro against a panel of human tumor cell lines. The results suggest that the electron-withdrawing group on the aza-brazilan moiety, substituted 5,6-dimethyl-benzimidazole ring and substitution of the imidazolyl-3-position with a 4-methylbenzyl group were essential for modulating the cytotoxic activity. Compounds 55 and 39, bearing a 4-methylbenzyl substituent at position-3 of 5,6-dimethyl-benzimidazole, were found to be the most potent compounds with IC50 values of 0.52-1.30 μM and 0.56-1.51 μM against four human tumor cell lines investigated. Particularly, compound 57 exhibited inhibitory activity against the MCF-7 cell line with an IC50 value of 0.35 μM and was 56-fold more sensitive than DDP. Moreover, compound 55 inhibited cell proliferation through inducing G0/G1 cell cycle arrest and apoptosis in SMMC-7721 cells.
- Huang, Mingqin,Duan, Shengzu,Ma, Xueqiong,Cai, Bicheng,Wu, Dongmei,Li, Yan,Li, Liang,Zhang, Hongbin,Yang, Xiaodong
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p. 1027 - 1036
(2019/06/27)
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- The Employment of Sodium Hydride as a Michael Donor in Palladium-catalyzed Reductions of α, β-Unsaturated Carbonyl Compounds
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Sodium hydride was employed as a Michael donor under the catalysis of PdCl2 for 1,4-conjugate reductions of α, β-unsaturated carbonyl compounds, which features operational simplicity, mild conditions and high atom-economy. The merits of NaH as a reductant were demonstrated by the one-pot or cascade reactions for the syntheses of complex molecules. (Figure presented.).
- Liu, Ye,Mao, Yujian,Hu, Yanwei,Gui, Jingjing,Wang, Liang,Wang, Wei,Zhang, Shilei
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supporting information
p. 1554 - 1558
(2019/02/16)
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- Silica Gel-mediated Synthesis of β-Enamino Esters and its Application for the Synthesis of Indeno 4-Hydroxypyridin-2(1H)-Ones
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The full scope of SiO2-based condensation of aliphatic or aromatic amines and β-keto esters to give β-enamino esters was examined. Functionalized linear β-enamino esters were easily obtained from SiO2-based condensation of β-keto esters and amines only after simple filtration. It was also demonstrated that cyclic β-enamino esters with 99% purity can be prepared in a practically large scale (60 g) without using silica gel column chromatography. The utility of the present method was fortified by the preparation of pharmaceutically useful indeno-4-hydroxypyridin-2(1H)-one analogue 11.
- Kim, Soong-Hyun,Bae, Seri,Ko, Eun Bi,Park, Ga Young,Lee, Eunhye,Hwang, Hee Jong,Im, Chun Young,Song, Minsoo
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p. 262 - 269
(2019/02/09)
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- Ethynylbenziodazolones (EBZ) as Electrophilic Alkynylation Reagents for the Highly Enantioselective Copper-Catalyzed Oxyalkynylation of Diazo Compounds
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Ethynylbenziodoxol(on)e (EBX) cyclic hypervalent iodine reagents are now established reagents for the alkynylation of radicals and nucleophiles, yet they present limited possibilities for further structure and reactivity modification. Herein, the first synthesis is reported for the corresponding ethynylbenziodazolone (EBZ) reagents, in which the oxygen atom in the iodoheterocycle is replaced by a nitrogen atom. The substituent on the nitrogen enables further fine-tuning of the reagent structure and reactivity. EBZ reagents are obtained easily from the corresponding benzamides by using a one-step procedure, and display reactivity comparable to that of EBX reagents. In particular, they are applied in an asymmetric copper-catalyzed oxyalkynylation of diazo compounds, which proceeds in high yield and enantioselectivity for a broad range of substituents on the diazo compounds and the alkyne.
- Hari, Durga Prasad,Schouwey, Lionel,Barber, Verity,Scopelliti, Rosario,Fadaei-Tirani, Farzaneh,Waser, Jerome
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supporting information
(2019/05/28)
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- Lanthanum-Catalyzed Enantioselective Trifluoromethylation by Using an Electrophilic Hypervalent Iodine Reagent
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A highly enantioselective catalytic method for the synthesis of quaternary α-trifluoromethyl derivatives of 3-oxo esters is described. The reaction uses lanthanum(III) triflate and chiral PyBOX-type C2-symmetric ligands to generate intermediate LaIII complexes that incorporate an enolate moiety of the starting 3-oxo ester and the trifluoromethylation transfer reagent. The enantioselectivity of the reaction stems from the efficient blockage of one of the prochiral faces of the LaIII enolate by one unit of the C2-symmetric ligand.
- Granados, Albert,Rivilla, Iván,Cossío, Fernando P.,Vallribera, Adelina
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supporting information
p. 8214 - 8218
(2019/05/15)
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- Highly Carbon-Selective Monofluoromethylation of β-Ketoesters with Fluoromethyl Iodide
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A highly carbon-selective monofluoromethylation of a broad range of β-ketoesters with fluoromethyl iodide under mild conditions is described. The uses of lithium tert-butoxide as the base and diglyme as the solvent made great contributions to the high C/O regioselectivity.
- Ding, Tianqi,Jiang, Lvqi,Yang, Jie,Xu, Yimin,Wang, Guixiang,Yi, Wenbin
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supporting information
p. 6025 - 6028
(2019/08/20)
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- Method for preparing 1,3-dicarbonyl compound based on metal hydride/palladium compound system
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The invention discloses a method for preparing a 1,3-dicarbonyl compound based on a metal hydride/palladium compound system. The method comprises the following steps: making a palladium compound and metal hydride suspend in a solvent under the protection
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Paragraph 0019-0026
(2019/01/08)
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- Application of metal hydride/ palladium compound system in preparing 1,3-dicarbonyl compound through cascade reaction in electron-deficient alkene compound
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The invention discloses application of a metal hydride/ palladium compound system in preparing a 1,3-dicarbonyl compound through cascade reaction in an electron-deficient alkene compound. The reactioncomprises the following steps of under the protection o
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Paragraph 0019-0026
(2019/01/14)
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- Synthesis of a Bolm's 2,2′-Bipyridine Ligand Analogue and Its Applications
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A new method of synthesis of an analogue of Bolm's 2,2′-bipyridine ligand based on the catalytic [2+2+2] cyclotrimerization of 1-halodiynes with nitriles was developed. Crucial step of the whole synthesis turned out to be homodimerization of a substituted 2-bromopyridine to the corresponding bipyridine, that was studied and optimized. The newly prepared bipyridine (S,S)-2 was then tested as a chiral ligand in metal-catalyzed enantioselective reactions. Out of the studied reactions the most promising results were obtained in epoxide ring opening (82% yield, 98% ee) and Mukaiyama aldol reaction (>96% yield, 99/1 dr, 92% ee). In the case of Mukaiyama-aldol reaction as well as in the Michael addition, novel ligand 2 proved its robustness compared to Bolm's ligand as it was less sensitive to the purity of used reagents. (Figure presented.).
- Bedná?ová, Eva,Dra?ínsky, Martin,Malatinec, ?tefan,Císa?ová, Ivana,Lamaty, Frédéric,Kotora, Martin
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supporting information
p. 2869 - 2878
(2018/08/17)
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- Reinventing the de Mayo reaction: Synthesis of 1,5-diketones or 1,5-ketoesters via visible light [2+2] cycloaddition of β-diketones or β-ketoesters with styrenes
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A visible light mediated De Mayo reaction between 1,3-diketones and styrenes following a [2+2] cycloaddition pathway via a photosensitization mechanism gives access to 1,5-diketones. The reaction has been applied to substituted styrenes and aryl- and alkyl-substituted ketones. Moreover, the method converts β-ketoesters, β-amido esters, and β-cyano ketones. Seven membered rings, a frequent structural motif of natural products, are also accessible using this methodology.
- Martinez-Haya, Rebeca,Marzo, Leyre,K?nig, Burkhard
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supporting information
p. 11602 - 11605
(2018/10/31)
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- Iron-Catalyzed Acyl Migration of Tertiary α-Azidyl Ketones: Synthetic Approach toward Enamides and Isoquinolones
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This paper reports that tertiary α-azidyl phenyl ketones can be transformed into enamides by treatment with FeBr2 at elevated temperature in DMF. The reaction proceeds via 1,2-benzoyl migration from α-carbon to the nitrogen atom, accompanied by expulsion of a nitrogen molecule. This protocol is suitable for the synthesis of N-(cyclopent-1-en-1-yl)benzamides, N-(cyclohex-1-en-1-yl)benzamides, and N-benzoyl-α-methyl enamines and provides a convenient approach toward isoquinolones.
- Yang, Tonghao,Fan, Xing,Zhao, Xiaopeng,Yu, Wei
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supporting information
p. 1875 - 1879
(2018/04/16)
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- Asymmetric Alkynylation of β-Ketoesters and Naphthols Promoted by New Chiral Biphenylic Iodanes
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The preparation of new chiral biphenylic λ3-iodane reagents bearing transferable alkynyl ligands is described. These reagents transfer their carbon-based ligands onto β-ketoesters with an enantiomeric excess (ee) up to 68 %, and most remarkably, enable the dearomative alkynylation of naphthols in good to high yields up to 84 % ee.
- Companys, Simon,Peixoto, Philippe A.,Bosset, Cyril,Chassaing, Stefan,Miqueu, Karinne,Sotiropoulos, Jean-Marc,Pouységu, Laurent,Quideau, Stéphane
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supporting information
p. 13309 - 13313
(2017/10/05)
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- Highly Enantioselective α-Cyanation with 4-Acetylphenyl Cyanate
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A highly effective asymmetric version of α-cyanation of β-keto esters and amides was developed with a Lewis-acid catalyst. Thus, by using 10 mol % of a tridentate bisoxazoline–zinc(II) complex as the catalyst, a series of chiral nitriles containing a quaternary carbon center were obtained in excellent enantioselectivities (up to 97 % enantiomeric excess) and up to 95 % yield in the presence of 4 ? molar sieve at room temperature. For the first time, mild and active 4-acetylphenyl cyanate was used instead of cyano-hyperiodinate as the cationic cyano source for catalytic asymmetric α-cyanation.
- Qiu, Jia-Shen,Wang, Yao-Feng,Qi, Gui-Rong,Karmaker, Pran G.,Yin, Hong-Quan,Chen, Fu-Xue
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supporting information
p. 1775 - 1778
(2017/02/15)
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- Chiral N,N'-Dioxide Organocatalyzed Asymmetric Electrophilic α-Cyanation of β-Keto Esters and β-Keto Amides
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An enantioselective electrophilic α-cyanation of 1-indanone-derived β-keto esters and β-keto amides using a hypervalent iodine as the cyanide-transfer reagent was realized. A chiral N,N'-dioxide was used as the efficient bifunctional organocatalyst in the presence of inorganic base, which gave the corresponding α-cyano dicarbonyl compounds in yields of 50-99% with good enantioselectivities (87-97% ee).
- Ma, Baiwei,Lin, Xiaobin,Lin, Lili,Feng, Xiaoming,Liu, Xiaohua
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p. 701 - 708
(2017/04/26)
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- Enantioselective electrophilic cyanation of β-keto amides catalysed by a cinchona organocatalyst
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An operationally simple protocol for the enantioselective electrophilic α-cyanation of β-keto amides catalyzed by cinchona-derived catalysts has been demonstrated. The resulting products could be obtained with good to high enantioselectivities (up to 88% ee) and with excellent yields (up to 94%) by employing the mild active 4-acetylphenyl cyanate as the cationic cyano source in the catalytic asymmetric α-cyanation reaction.
- Karmaker, Pran Gopal,Qiu, Jiashen,Wu, Di,Reng, Mengmeng,Yang, Zhuo,Yin, Hongquan,Chen, Fu-Xue
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supporting information
p. 7753 - 7757
(2017/10/06)
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- Structure-dependent selective O- or C-trifluoroethylation of 1,3-dicarbonyls by mesityl(2,2,2-trifluoroethyl)iodonium triflate
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Reaction of [ArICH2CF3][OTf] with structurally diversified 1,3-dicarbonyls and an appropriate base at room temperature gave O-trifluoroethylated products, C-trifluoroethylated products, or a mixture of O- and C-trifluoroethylated products in good yields. The product type was dramatically dependent upon the structure of the starting 1,3-dicarbonyls in this reaction. The cyclic 1,3-diketones exclusively afforded the O-trifluoroethylated products, whereas the acyclic 1,3-diketones, β-keto esters, and malonates selectively or specifically formed the C-trifluoroethylated products. Li2CO3 facilitated the C-trifluoroethylation of acyclic 1,3-diketones and β-keto esters. The reaction proceeded under mild conditions, without pre-activation of 1,3-dicarbonyls and use of strong base, and demonstrated a catalyst-free structure-dependent regioselective trifluoroethylation of 1,3-dicarbonyls by mesityl(2,2,2-trifluoroethyl)iodonium triflate.
- Zhao, Cheng-Long,Yang, Jing,Han, Zhou-Zhou,Zhang, Cheng-Pan
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supporting information
p. 23 - 30
(2017/10/30)
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- Copper-Catalysed Decarboxylative Trifluoromethylation of β-Ketoacids
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An efficient method for Cu-catalyzed decarboxylative trifluoromethylation of β-ketoacids to achieve α-trifluoromethyl ketones was developed. A wide variety of synthetically useful α-trifluoromethyl ketones were obtained in modest to good yields under mild reaction conditions. The present method also exhibits good functional-group compatibility.
- Xu, Xiaolan,Chen, Huanhuan,He, Jianbo,Xu, Huajian
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supporting information
p. 1665 - 1668
(2017/10/05)
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- Synthesis of 1,4-Diketones from β-Oxo Esters and Enol Acetates by Cerium-Catalyzed Oxidative Umpolung Reaction
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Cyclic β-oxo esters are converted with enol acetates in a cerium-catalyzed, oxidative Umpolung reaction to furnish 1,4-diketones with up to 95 % yield. Atmospheric oxygen is the oxidant in this process, which can be regarded as ideal from economic and ecological points of view. Further advantages of this new C-C coupling reaction are its operational simplicity and the application of nontoxic and inexpensive CeCl3·7H2O as precatalyst.
- Geibel, Irina,Christoffers, Jens
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supporting information
p. 918 - 920
(2016/03/01)
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- Cooperative Indium(III)/Silver(I) System for Oxidative Coupling/Annulation of 1,3-Dicarbonyls and Styrenes: Construction of Five-Membered Heterocycles
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A cooperative indium(III)/silver(I) system for the synthesis of various five-membered heterocycles, including dihydrofurans, pyrroles, spirolactones, and spiroiminolactones, through the sequential oxidative coupling/annulation reaction of 1,3-dicarbonyl compounds with styrenes has been developed. Four different heterocyclic systems were successfully synthesized depending on the substitution pattern of the substrates using readily available starting materials. This system has the advantages of a broad substrate scope, moderate to good chemical yields, an operationally easy and simple procedure, and short reaction times. (Figure presented.) .
- Ko, Tae Yun,Youn, So Won
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supporting information
p. 1934 - 1941
(2016/07/06)
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- Trimethylchlorosilane-Mediated Mild α-Chlorination of 1,3-Dicarbonyl Compounds Promoted by Phenyliodonium Diacetate
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Trimethylchlorosilane was used as chlorine source for the α-chlorination of 1,3-dicarbonyl compounds with phenyliodonium diacetate as oxidant at room temperature. The reaction allows the selective synthesis of α-monochlorinated products from different kinds of 1,3-dicarbonyl compounds in good yield. The potential possibility of this conversion for bromination has also been investigated.
- Chong, Siying,Su, Yingpeng,Wu, Lili,Zhang, Weigang,Ma, Junyan,Chen, Xiaowei,Huang, Danfeng,Wang, Ke-Hu,Hu, Yulai
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supporting information
p. 1359 - 1370
(2016/05/02)
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- Facile Synthesis of Spirocyclic Lactams from β-Keto Carboxylic Acids
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A facile synthesis of spirocyclic lactams starting from β-keto carboxylic acids via a one-pot cascade reaction involving a Curtius rearrangement and an intramolecular nucleophilic addition of the enol carbon to the isocyanate intermediate is reported. The same conditions have also been used for the generation of fused cyclic lactams with similar good yields. The synthetic value of this method has been demonstrated by efficient synthesis of tetracyclic spirolactam 8 and pentacyclic spirolactam 9.
- Yang, Wei,Sun, Xianyu,Yu, Wenbo,Rai, Rachita,Deschamps, Jeffrey R.,Mitchell, Lauren A.,Jiang, Chao,Mackerell, Alexander D.,Xue, Fengtian
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supporting information
p. 3070 - 3073
(2015/06/30)
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- Bifunctional Thiourea Catalyzed Asymmetric Mannich Reaction Using Trifluoromethyl Aldimine as Trifluoromethyl Building Blocks
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An efficient bifunctional thiourea catalyzed asymmetric Mannich reaction with trifluoromethyl aldimine as trifluoromethyl building block was achieved to give the products in good diastereoselectivity and enantioselectivity.
- Ji, Shilong,Alkhalil, Ahmed Ebrahim,Su, Yingpeng,Xia, Xiaowen,Chong, Siying,Wang, Ke-Hu,Huang, Danfeng,Fu, Ying,Hu, Yulai
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supporting information
p. 1725 - 1731
(2015/07/20)
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- New Monocyclic, Bicyclic, and Tricyclic Ethynylcyanodienones as Activators of the Keap1/Nrf2/ARE Pathway and Inhibitors of Inducible Nitric Oxide Synthase
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A monocyclic compound 3 (3-ethynyl-3-methyl-6-oxocyclohexa-1,4-dienecarbonitrile) is a highly reactive Michael acceptor leading to reversible adducts with nucleophiles, which displays equal or greater potency than the pentacyclic triterpenoid CDDO in inflammation and carcinogenesis related assays. Recently, reversible covalent drugs, which bind with protein targets but not permanently, have been gaining attention because of their unique features. To explore such reversible covalent drugs, we have synthesized monocyclic, bicyclic, and tricyclic compounds containing 3 as an electrophilic fragment and evaluated them as activators of the Keap1/Nrf2/ARE pathway and inhibitors of iNOS. Notably, these compounds maintain the unique features of the chemical reactivity and biological potency of 3. Among them, a monocyclic compound 5 is the most potent in these assays while a tricyclic compound 14 displays a more robust and specific activation profile compared to 5. In conclusion, we demonstrate that 3 is a useful electrophilic fragment for exploring reversible covalent drugs. (Chemical Equation Presented).
- Li, Wei,Zheng, Suqing,Higgins, Maureen,Morra, Rocco P.,Mendis, Anne T.,Chien, Chih-Wei,Ojima, Iwao,Mierke, Dale F.,Dinkova-Kostova, Albena T.,Honda, Tadashi
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supporting information
p. 4738 - 4748
(2015/06/30)
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- Design, synthesis and structure-activity relationship of indoxacarb analogs as voltage-gated sodium channel blocker
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Indoxacarb, the first commercialized pyrazoline-type sodium-channel blocker, is a commonly used insecticide because of high selectivity. To discover sodium-channel blocker with high insecticidal activity, a series of novel indoxacarb analogs were designed and synthesized by judicious structural modifications of the substituent group of C5, C6 in indenone and C′4 in benzene ring. Some analogs exhibited significant insecticidal activities against Spodoptera litura F. and excellent BgNav1-1a channel inhibitory activity. The structure-activity analysis indicated that the presence of strong electron-withdrawing group and decreased steric hindrance of indenone ring (R1, R2) in 5- and 6-position could enhance larvicidal activity and BgNav1-1a channel inhibitory activity.
- Hao, Wenbo,Fu, Chunling,Yu, Huijuan,Chen, Jian,Xu, Hanhong,Shao, Guang,Jiang, Dingxin
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supporting information
p. 4576 - 4579
(2015/10/12)
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- Iron(iii)-salan complexes catalysed highly enantioselective fluorination and hydroxylation of β-keto esters and N-Boc oxindoles
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Chiral iron(iii)-salan complexes catalysed highly enantioselective α-fluorination and α-hydroxylation of β-keto esters and N-Boc oxindoles to give the corresponding products in high yields and good-to-excellent ee values under mild reaction conditions. This journal is the Partner Organisations 2014.
- Gu, Xin,Zhang, Yan,Xu, Zhen-Jiang,Che, Chi-Ming
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supporting information
p. 7870 - 7873
(2014/07/08)
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- Organocatalytic enantioselective allylic alkylation of MBH carbonates with β-keto esters
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The highly stereoselective allylic alkylation of Morita-Baylis-Hillman carbonates with β-ketoesters catalysed by β-ICD is described. The corresponding products containing two adjacent quaternary and tertiary carbon centers were obtained in good yields with high diastereoselectivity (up to 10 : 1 dr) and enantioselectivity (up to 95% ee).
- Kamlar,Hybelbauerova,Cisarova,Vesely
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supporting information
p. 5071 - 5076
(2014/07/08)
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- Enantioselective fluorination of ?-ketoesters catalyzed by chiral sodium phosphate: Remarkable enhancement of reactivity by simultaneous utilization of metal enolate and metal phosphate
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A highly enantioselective fluorination of ?-ketoesters catalyzed by chiral sodium phosphate is achieved. In this process, the simultaneous formation of sodium enolate and sodium phosphate under basic conditions is the key to achieving excellent selectivity. Indanone derivatives as well as benzofuranone derivatives could be employed in this reaction to afford the fluorinated adducts in good yields with good to excellent enantioselectivities.
- Mori, Keiji,Miyake, Ayaka,Akiyama, Takahiko
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supporting information
p. 137 - 139
(2014/01/23)
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- Catalytic asymmetric cross-dehydrogenative coupling: Activation of C-H bonds by a cooperative bimetallic catalyst system
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A cooperative bimetallic catalyst system was applied in the catalytic asymmetric cross-dehydrogenative coupling of β-ketoesters and xanthene. Various optically active xanthene derivatives bearing a quaternary stereogenic carbon center were obtained in moderate to good yields (up to 90%) with excellent enantioselectivities (up to 99% ee). Meanwhile, a transition-state model was proposed to explain the origin of the asymmetric induction.
- Cao, Weidi,Liu, Xiaohua,Peng, Ruixue,He, Peng,Lin, Lili,Feng, Xiaoming
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p. 3470 - 3472
(2013/05/23)
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- A new mild method for the C-acylation of ketone enolates. a convenient synthesis of β-keto-esters,-thionoesters, and-thioesters
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A new method for ketone enolate C-acylation is described which utilizes alkyl pentafluorophenylcarbonates, thiocarbonates, and thionocarbonates as the reactive acylating agents, and MgBr2·Et2O, DMAP, and i-Pr2NEt as the reagents for enolization. A wide range of ketones have been observed to undergo clean C-acylation via this protocol.
- Hale, Karl J.,Grabski, Milosz,Flasz, Jakub T.
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supporting information
p. 370 - 373
(2013/03/13)
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- Ethynylbenziodoxolones (EBX) as reagents for the ethynylation of stabilized enolates
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Herein, we report a detailed study on the electrophilic alkynylation of cyclic keto esters and amides with ethynylbenziodoxolone (EBX) reagents. The structure and stability of this class of reagents is first described more in details. Differential scannin
- Fernandez Gonzalez, Davinia,Brand, Jonathan P.,Mondiere, Regis,Waser, Jerome
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supporting information
p. 1631 - 1639
(2013/07/05)
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- Azidation of β-keto esters and silyl enol ethers with a benziodoxole reagent
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The efficient azidation of β-keto esters and silyl enol ethers using a benziodoxole-derived azide transfer reagent is reported. The azidation of cyclic β-keto esters could be achieved in up to quantitative yields in the absence of any catalyst. In the case of less reactive linear β-keto esters and silyl enol ethers, complete conversion and good yields could be obtained by using a zinc catalyst.
- Vita, Maria Victoria,Waser, Jerome
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supporting information
p. 3246 - 3249
(2013/07/26)
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- Solvent effect in reactions using strykers reagent
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The solvent has a significant influence in the rate of reactions promoted by Strykers reagent. The reactions performed in THF were, in most cases, faster than in toluene.
- Sass, Daiane Cristina,Heleno, Vladimir Constantino Gomes,Cavalcante, Simone,Da Silva Barbosa, Jader,Soares, Ana Carolina Ferreira,Constantino, Mauricio Gomes
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p. 9374 - 9378
(2013/01/15)
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- Tandem reduction + cyclization of ortho-substituted cinnamic esters
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Conjugate reduction of ortho-substituted cinnamic esters by Stryker's reagent to form copper enolates, followed by intramolecular aldol-type cyclization, successfully generated indane and tetralin rings in one pot efficiently. This tandem reaction is generally diastereoselective and provides good yields.
- Sass, Daiane Cristina,De Lucca Jr., Emílio Carlos,Da Silva Barbosa, Jader,De Oliveira, Kleber Thiago,Constantino, Mauricio Gomes
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p. 5371 - 5374
(2011/10/31)
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