- Reactions of donor-acceptor cyclopropanes or benzylidenemalonate with benzyl azide by generating gallium trichloride 1,2-zwitterionic complexes
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The reactions of 1,2-zwitterionic complexes, generated from 2-arylcyclopropane-1,1-dicarboxylates (ACDC) or benzylidenemalonate and gallium trichloride, with benzyl azide proceeds as a formal [3+2] cycloaddition to form dihydro-1,2,3-triazoles. The latter, when the reaction mixture is treated with 10% aqueous HCl, undergo retrocyclization with elimination of diazomalonate. The reaction of ACDC, benzyl azide, and GaCl3 with simultaneous mixing of the reagents leads to the interception of the 1,3-zwitterion, with this stage being accompanied by both the cyclization to substituted 1,2,3-triazinine and the elimination of a nitrogen molecule to form 3,4-dihydro-2H-1,2-oxazine structure, which after acid hydrolysis gives substituted 3-hydroxypyrrolidin-2-one.
- Borisova,Tarasova,Potapov,Novikov,Tomilov, Yu. V.
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Read Online
- 4,5-Dialkyl-substituted 3-oxo-(2H)-isothiazole 1,1-dioxides in reactions with diazomethane
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It has been established that the interaction of diazomethane with 4,5-dialkyl-substituted 3-oxo-(2H)-isothiazole 1,1-dioxides proceeds in two stages. Initially alkylation of the sulfonimide nitrogen atom and the carbonyl group oxygen atom occurs (in a ratio of ~ 3:2), then there is a regioselective cycloaddition of diazomethane at the C=C double bond with the formation of the corresponding N-methyloxoisothiazolopyrazolines and 3-methoxyisothiazolopyrazolines.
- Rodina,Gidon,Nikolaev,Shulze
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Read Online
- A Cyclopropene Electrophile that Targets Glutathione S-Transferase Omega-1 in Cells
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Cyclopropenes are an important new addition to the portfolio of functional groups that can be used for bioorthogonal couplings. The inert nature of these highly strained compounds in complex biological systems is almost counterintuitive given their established electrophilic properties in organic synthesis. Here we provide the first demonstration of a cyclopropene that is capable of direct conjugation to protein targets in cells and show that this compound preferentially alkylates the active site cysteine of glutathione S-transferase omega-1 (GSTO1).
- W?rmer, Gustav J.,Hansen, Bente K.,Palmfeldt, Johan,Poulsen, Thomas B.
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- A Practical Synthesis of Valuable Strained Eight-Membered-Ring Derivatives for Click Chemistry
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A convenient and cost-effective synthetic access to cyclooctyne and trans-cyclooctene derivatives is described. A cyclopropanation step using copper powder in place of Rh2(OAc)4 as catalyst and a symmetric diazomalonate resulted in a drastic decrease in the overall cost of the synthesis. Further derivatizations allowed us to characterize, for the first time, the structure of a BCN analogue by X-ray crystallography, and to obtain a library of derivatives that could potentially be useful for applications in metal-free click chemistry.
- Bernard, Sabrina,Kumar, Ramar Arun,Porte, Karine,Thuéry, Pierre,Taran, Frédéric,Audisio, Davide
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- Two Catalytic Methods of an Asymmetric Wittig [2,3]-Rearrangement
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Two different approaches for asymmetric catalytic Wittig [2,3]-rearrangement were developed. Allyloxymalonate derivatives were converted into homoallyl alcohols via organocatalytic or Ca2+-catalyzed pathways in moderate to high enantioselectivi
- O?eka, Maksim,Kimm, Mariliis,J?rving, Ivar,Lippur, Kristin,Kanger, T?nis
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Read Online
- Selective Chain-End Functionalization of Polar Polyethylenes: Orthogonal Reactivity of Carbene and Polar Vinyl Monomers in Their Copolymerization with Ethylene
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Pd(II)-catalyzed copolymerization of ethylene, carbene species, and polar vinyl monomers is successfully developed for the first time to obtain chain-end-functionalized polar polyethylenes, with selective distribution of the polar vinyl monomers within the main chain and carbene at the chain-end. Notably, >99% chain-end-capping with the carbene species can be achieved under the optimized conditions. Mechanistic investigations suggest that the carbene precursor reacts with the generated alkyl palladium complex to terminate the growing chain-end and regenerate the catalyst.
- Wang, Xiaoming,Nozaki, Kyoko
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Read Online
- Selective Alkynylallylation of the C?C σ Bond of Cyclopropenes
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A Pd-catalyzed regio- and stereoselective alkynylallylation of a specific C?C σ bond in cyclopropenes, using allyl propiolates as both allylation and alkynylation reagents, has been achieved for the first time. By merging selective C(sp2)-C(sp3) bond scission with conjunctive cross-couplings, this decarboxylative reorganization reaction features fascinating atom and step economy and provides an efficient approach to highly functionalized dienynes from readily available substrates. Without further optimization, gram-scale products can be easily obtained by such a simple, neutral, and low-cost catalytic system with high TONs. DFT calculations afford a rationale toward the formation of the products and indicate that the selective insertion of the double bond of cyclopropenes into the C-Pd bond of ambidentate Pd complex and the subsequent nonclassical β-C elimination promoted by 1,4-palladium migration are critical for the success of the reaction.
- Chen, Ying-Chun,Jiang, Zeqi,Niu, Sheng-Li,Ouyang, Qin,Xiao, Qing,Zeng, Qiang
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supporting information
p. 297 - 303
(2020/11/30)
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- Azide Radical Initiated Ring Opening of Cyclopropenes Leading to Alkenyl Nitriles and Polycyclic Aromatic Compounds
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We report herein a radical-mediated amination of cyclopropenes. The transformation proceeds through a cleavage of the three-membered ring after the addition of an azide radical on the strained double bond and leads to tetrasubstituted alkenyl nitrile derivatives upon loss of N2. With 1,2-diaryl substituted cyclopropenes, this methodology could be extended to a one-pot synthesis of highly functionalized polycyclic aromatic compounds (PACs). This transformation allows the synthesis of nitrile-substituted alkenes and aromatic compounds from rapidly accessed cyclopropenes using only commercially available reagents.
- Muriel, Bastian,Waser, Jerome
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supporting information
p. 4075 - 4079
(2021/01/18)
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- Borane Catalyzed Selective Diazo Cross-Coupling Towards Pyrazoles
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Decomposition of donor-acceptor diazo compounds leads to the formation of reactive carbene intermediates. These can undergo a wide variety of carbene transfer reactions to yield synthetically useful products. Herein, we report a selective borane catalyzed cyclization reaction from the combination of two different diazo compounds to afford N-substituted pyrazoles. The selective decomposition of the more reactive α-aryl α-diazoester and subsequent reaction with a vinyl diazoacetate produces N-alkylated pyrazoles in a regioselective manner. Catalytic amounts of tris(pentafluorophenyl)borane (10 mol%) were employed to afford the pyrazole products (36 examples) in yields from 59 to 80%. Extensive DFT studies have been undertaken to interpret the mechanism for this reaction which was found to go through two tandem catalytic cycles, both catalyzed by B(C6F5)3.
- Ariafard, Alireza,Babaahmadi, Rasool,Dasgupta, Ayan,Gierlichs, Lukas,Melen, Rebecca L.,Pahar, Sanjukta,Yates, Brian F.
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- Iridium(III)-Catalyzed C(3)-H Alkylation of Isoquinolines via Metal Carbene Migratory Insertion
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An Ir(III)-catalyzed C(3)-H alkylation of N-acetyl-1,2-dihydroisoquinolines with diverse acceptor-acceptor diazo compounds has been achieved under a single catalytic system via metal carbene migratory insertion. Moreover, further synthetic transformations of the alkylated products such as aromatization, selective decarboxylation, and decarbonylation lead to the formation of several synthetically viable isoquinoline derivatives having immense potentials.
- Jha, Neha,Singh, Roushan Prakash,Saxena, Paridhi,Kapur, Manmohan
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supporting information
p. 8694 - 8698
(2021/11/24)
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- Amino-modified Merrifield resins as recyclable catalysts for the safe and sustainable preparation of functionalized α-diazo carbonyl compounds
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Amino-functionalized polystyrene polymers derived from Merrifield resins were prepared and characterized. These basic materials were successfully employed as heterogeneous catalysts in the diazo transfer reaction to 1,3-dicarbonyl compounds, furnishing the corresponding diazo compounds in good to excellent yields and in relatively short reaction times. In addition, the work-up and purification protocols are simple and do not generate large amounts of waste, which are important features in sustainable catalysis and environmentally benign processes. The feasibility of the recovery and reuse of the amino-modified catalysts was also verified, since they can be employed up to five times without appreciable loss of catalytic activity. This straightforward procedure can be readily scaled up to gram scale, enabling the wide application of this method. The synthetic potential was demonstrated through the two-step preparation of 2-amino-N-dodecylacetamide (ANDA), a small molecule of commercial relevance.
- Fantinel, Mariane,Valiati, Nayara,Moro, Pedro A.M.,Sá, Marcus M.
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- Rhodium-Catalyzed [4+2] Annulation of N-Aryl Pyrazolones with Diazo Compounds To Access Pyrazolone-Fused Cinnolines
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An efficient synthesis of novel dinitrogen-fused heterocycles such as pyrazolo[1,2-a]cinnoline derivatives have been accomplished by the rhodium(III)-catalyzed reaction of N-arylpyrazol-5-ones with α-diazo compounds. This reaction proceeds through a cascade C?H activation/intramolecular cyclization with a broad substrate scope. Furthermore, this protocol is successfully extended to the unusual phosphorus-containing α-diazo compounds and cyclic diazo compounds as the cross-coupling partners to deliver the two new kinds of pyrazolo[1,2-a]cinnolinones. The control experiments were performed to reveal insight into the mechanism of this reaction, involving reversible C?H activation, migratory insertion of the diazo compound, and cascade cyclization as the key steps of the transformation. Moreover, gram-scale synthesis and further transformation of the target product demonstrate the synthetic utility of the present protocol.
- Dhole, Sandip,Huang, Wan-Wen,Huang, Ying-Ti,Lin, Chih-Yu,Sun, Chung-Ming
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supporting information
p. 4984 - 4992
(2021/09/28)
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- Electrosynthesis of Dihydropyrano[4,3-b]indoles Based on a Double Oxidative [3+3] Cycloaddition
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Oxidative [3+3] cycloadditions offer an efficient route for six-membered-ring formation. This approach has been realized based on an electrochemical oxidative coupling of indoles/enamines with active methylene compounds followed by tandem 6π-electrocyclization leading to the synthesis of dihydropyrano[4,3-b]indoles and 2,3-dihydrofurans. The radical–radical cross-coupling of the radical species generated by anodic oxidation combined with the cathodic generation of the base from O2 allows for mild reaction conditions for the synthesis of structurally complex heterocycles.
- Choi, Subin,Park, Cheol-Min,Park, Jinhwi,Sim, Jeongwoo,Yu, Eunsoo
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supporting information
p. 11886 - 11891
(2020/05/22)
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- COMPOUNDS FOR THE TREATMENT OF KINASE-DEPENDENT DISORDERS
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Disclosed herein are compounds of Formula (I) which inhibit, regulate and/or modulate tyrosine kinase receptors, particularly Axl and Mer signal transduction pathways related to the changes in cellular activities, compositions containing the compounds, methods of using the compounds to treat kinase-dependent diseases and conditions, and methods for making the compounds.
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Paragraph 000353
(2020/12/29)
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- Tridentate Nickel(II)-Catalyzed Chemodivergent C-H Functionalization and Cyclopropanation: Regioselective and Diastereoselective Access to Substituted Aromatic Heterocycles
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A Schiff-base nickel(II)-phosphene-catalyzed chemodivergent C-H functionalization and cyclopropanation of aromatic heterocycles is reported in moderate to excellent yields and very good regioselectivity and diastereoselectivity. The weak, noncovalent interaction between the phosphene ligand and Ni center facilitates the ligand dissociation, generating the electronically and coordinatively unsaturated active catalyst. The proposed mechanisms for the reported reactions are in good accord with the experimental results and theoretical calculations, providing a suitable model of stereocontrol for the cyclopropanation reaction.
- Nag, Ekta,Gorantla, Sai Manoj N. V. T.,Arumugam, Selvakumar,Kulkarni, Aditya,Mondal, Kartik Chandra,Roy, Sudipta
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supporting information
p. 6313 - 6318
(2020/09/02)
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- Kinetic Resolution of Propargylic Ethers via [2,3]-Wittig Rearrangement to Synthesize Chiral α-Hydroxyallenes
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An efficient kinetic resolution of propargyloxy dicarbonyl compounds via asymmetric [2,3]-Wittig rearrangement was achieved by using a chiral N,N′-dioxide/NiII complex catalyst. Various chiral α-allenyl alcohols were obtained in high enantioselectivities under mild conditions. The utility of this method was readily demonstrated in the asymmetric synthesis of the chiral 2,5-dihydrofuran derivative.
- Xu, Xi,Dong, Shunxi,Feng, Lili,Wang, Sijing,Liu, Xiaohua,Feng, Xiaoming
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supporting information
p. 2692 - 2696
(2020/03/30)
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- Taking diazo transfer to water: α-diazo carbonyl compounds from in situ generated mesyl azide
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Mesyl azide generated in situ in aqueous medium converted a range of active methylene substrates into the corresponding diazo compounds in good yields and high purity with no need for chromatographic purification. The products thus obtained are suitable for the subsequent RhII-catalyzed O–H insertions with no need for chromatography in the interim.
- Dar'in, Dmitry V.,Krasavin, Mikhail,Shevalev, Robert M.,Zhmurov, Petr A.
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p. 372 - 373
(2020/06/19)
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- Triarylborane-Catalyzed Alkenylation Reactions of Aryl Esters with Diazo Compounds
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Herein we report a facile, mild reaction protocol to form carbon–carbon bonds in the absence of transition metal catalysts. We demonstrate the metal-free alkenylation reactions of aryl esters with α-diazoesters to give highly functionalized enyne products. Catalytic amounts of tris(pentafluorophenyl)borane (10–20 mol %) are employed to afford the C=C coupled products (31 examples) in good to excellent yields (36–87 %). DFT studies were used to elucidate the mechanism for this alkenylation reaction.
- Ariafard, Alireza,Babaahmadi, Rasool,Dasgupta, Ayan,Gierlichs, Lukas,Melen, Rebecca L.,Stefkova, Katarína
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supporting information
p. 15492 - 15496
(2020/07/20)
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- 3-(5-HYDROXY-1-OXOISOINDOLIN-2-YL)PIPERIDINE-2,6-DIONE DERIVATIVES AND USES THEREOF
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The present disclosure provides a compound of Formula (I′): or a pharmaceutically acceptable salt, hydrate, solvate, prodrug, stereoisomer, or tautomer thereof, wherein Rx, X1, X2, and R1 are as defined herein, and methods of making and using same.
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Paragraph 1687-1688
(2020/02/05)
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- Glycosylation Enabled by Successive Rhodium(II) and Br?nsted Acid Catalysis
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Herein, we reported on a highly efficient glycosylation reaction comprising two chronological meticulously designed catalytic cycles: (1) rhodium-catalyzed formation of sulfonium ylide and (2) Br?nsted acid-catalyzed formation of sulfonium ion. This protocol highlighted an effective and robust tactic to prepare a glycosyl sulfonium ion from a glycosyl sulfonium ylide precursor amenable for glycosylation.
- Meng, Lingkui,Wu, Peng,Fang, Jing,Xiao, Ying,Xiao, Xiong,Tu, Guangsheng,Ma, Xiang,Teng, Shuang,Zeng, Jing,Wan, Qian
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supporting information
p. 11775 - 11780
(2019/08/20)
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- A 'sulfonyl-azide-free' (SAFE) aqueous-phase diazo transfer reaction for parallel and diversity-oriented synthesis
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Diazo transfer reactions are notoriously associated with the use of potentially explosive sulfonyl azides. The first 'sulfonyl-azide-free' (SAFE) protocol for producing diazo compounds from their active-methylene precursors via the Regitz diazo transfer reaction was developed and has displayed a remarkable substrate scope. It can be applied to generating arrays of diazo compounds for further evolution via combinatorial chemistry and a range of scaffold-generating transformations.
- Dar'In, Dmitry,Kantin, Grigory,Krasavin, Mikhail
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supporting information
p. 5239 - 5242
(2019/05/08)
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- Rhodium(iii)-catalyzed sulfonamide directed ortho C-H carbenoid functionalization via metal carbene migratory insertion
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A rhodium(iii)-catalyzed sulfonamide directed ortho C-H carbenoid functionalization has been developed with good yields. This method is attractive due to its broad substrate scope, and enables derivation of diverse biologically active sulfonamide structures and late-stage modification of sulfa drugs.
- Dong, Yi,Chen, Jiajing,Xu, Heng
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supporting information
p. 2027 - 2030
(2019/02/19)
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- SULPHONAMIDES AND COMPOSITIONS THEREOF FOR TREATING CONDITIONS ASSOCIATED WITH NLRP ACTIVITY
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In one aspect, compounds of Formula AA, or a pharmaceutically acceptable salt thereof, are featured: wherein the variables shown in Formula AA can be as defined anywhere herein. Compounds AA are modulators of NLRP1 and/or NLRP3
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Page/Page column 535
(2019/05/10)
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- Catalyst-Controlled Chemodivergent Annulation to Indolo/Pyrrolo-Fused Diazepine and Quinoxaline
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Catalyst-controlled chemodivergent annulation between o-indolo anilines and diazo compounds has explored for the synthesis of indolo-fused diazepine and quinoxaline. Under the Rh(III) catalyst, reaction proceeded through the free amine assisted C2?H activation followed by amidation leading to the diazepino[1,7-a]indole in a highly selective manner. While with Ru(II) catalyst, reaction involves formation Ru?carbene complex followed by ?NH2 group insertion and cascade cyclization via metallo-ene type reaction, β-hydride elimination to furnish the indolo[1,2-a]quinoxaline as the predominating product. This strategy directs modular approach towards the construction of unique indolo-fused diazepine/quinoxaline as well as pyrrolo-fused diazepine/quinoxaline scaffolds in excellent yields. (Figure presented.).
- Dhole, Sandip,Chiu, Wei-Jung,Sun, Chung-Ming
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supporting information
p. 2916 - 2925
(2019/04/26)
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- Rhodium(i)-catalyzed vinylation/[2 + 1] carbocyclization of 1,6-enynes with α-diazocarbonyl compounds
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A sequential Rh(i)-catalyzed vinylation/[2 + 1]carbocyclization between enynes and diazo compounds has been developed. This transformation features a wide range of enynes and acceptor/acceptor diazo compounds, providing easy access to versatile vinyl-substituted azabicyclo[3.1.0]hexanes having a broad tolerance to functional groups.
- Huang, Junmin,Hu, Xinwei,Chen, Fengjuan,Gui, Jiao,Zeng, Wei
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supporting information
p. 7042 - 7054
(2019/08/01)
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- Rhodium(III)-Catalyzed Regioselective Direct C4-Alkylation and C2-Annulation of Indoles: Straightforward Access to Indolopyridone
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A straightforward RhIII-catalyzed strategy was developed for the site-selective C4-alkylation and C2-annulation of indole by using electronically variable diazo esters. The transformation was accomplished with the assist of an oxime directing group at the C3 position of the indole core with wide scope and functional-group tolerance. The method directly provided an indolopyridone core. The selectivity was triggered by the reactivity of the diazo coupling partner.
- Biswas, Aniruddha,Samanta, Rajarshi
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p. 1426 - 1436
(2018/04/06)
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- An Expeditious Route to trans-Configured Tetrahydrothiophenes Enabled by Fe(OTf)3-Catalyzed [3+2] Cycloaddition of Donor–Acceptor Cyclopropanes with Thionoesters
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A synthetic route to trans-configured tetrahydrothiophenes (THTs) through Fe(OTf)3-promoted [3+2] cycloaddition of donor–acceptor cyclopropanes with thionoesters was developed. The cycloaddition proceeded in high yield with high diastereoselectivity, affording transient α-alkoxy THTs. Not only aromatic and aliphatic thionoesters, but also thionolactone were applicable to the present iron catalysis. Further transformation of the S,O-ketal functionality of the product was achieved in a highly trans diastereoselective manner. Moreover, the utility of our methodology was clearly demonstrated by the synthesis of enantioenriched trans-configured THTs.
- Matsumoto, Yohei,Nakatake, Daiki,Yazaki, Ryo,Ohshima, Takashi
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supporting information
p. 6062 - 6066
(2018/03/28)
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- Rh(III)-Catalyzed Redox-Neutral Unsymmetrical C-H Alkylation and Amidation Reactions of N-Phenoxyacetamides
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A Rh(III)-catalyzed unsymmetrical C-H alkylation and amidation of N-phenoxyacetamides with diazo compounds has been developed under mild and redox-neutral conditions, producing dinitrogen as the only byproduct. The reaction represents the first example of one-step, unsymmetrical difunctionalization of two ortho-C-H bonds. Experimental and computational studies support that N-phenoxyacetamides most likely undergo an initial ortho-C-H alkylation with diazo compounds via a Rh(III)-catalyzed C-H activation, and the resulting Rh(III) intermediate subsequently undergoes an intramolecular oxidative addition into the O-N bond to form a Rh(V) nitrenoid species that is protonated and further directed toward electrophilic addition to the second ortho position of the phenyl ring. This work might provide a new direction for unsymmetrical C-H difunctionalization reactions in an efficient manner.
- Wu, Yunxiang,Chen, Zhaoqiang,Yang, Yaxi,Zhu, Weiliang,Zhou, Bing
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supporting information
p. 42 - 45
(2018/01/17)
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- Lewis Acid Catalyzed Enantioselective Desymmetrization of Donor–Acceptor meso-Diaminocyclopropanes
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The first Lewis acid catalyzed enantioselective ring-opening desymmetrization of a donor–acceptor meso-diaminocyclopropane is reported. The copper(II)-catalyzed Friedel–Crafts alkylation of indoles and one pyrrole with an unprecedented meso-diaminocyclopropane delivered enantioenriched, diastereomerically pure urea products, which are structurally related to natural and synthetic bioactive compounds. The development of a new ligand through the investigation of an underexplored subclass of bis(oxazoline) ligands was essential for achieving high enantioselectivities.
- Perrotta, Daniele,Wang, Ming-Ming,Waser, Jér?me
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supporting information
p. 5120 - 5123
(2018/03/27)
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- INDANE DERIVATIVES USEFUL AS MODULATORS OF MGLUR7
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The present invention provides compounds of formula (I) and pharmaceutically acceptable salts thereof, wherein n, X, Y, Z, D, R1, R2, R3, R4, R12, R15nd R16 are as defined in the specification, a process for their preparation, pharmaceutical compositions containing them and their use as modulators of mGluR7.
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Page/Page column 54-55
(2018/03/28)
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- Regioselective oxidative ring-opening of cyclopropenyl carboxylates by visible light photoredox catalysis
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Catalyzed by Ir(dFCF3ppy)2(dtbbpy)PF6, several aroyl methylidenemalonates were synthesized in good to excellent yields via visible light photoredox-catalyzed the oxidative ring-opening of cyclopropenyl carboxylate derivatives. The possible mechanism of oxidative quenching cycle was proposed.
- Ye, Qianwen,Ye, Hongqiang,Cheng, Dongping,Li, Xiaonian,Xu, Xiaoliang
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supporting information
p. 2546 - 2549
(2018/05/28)
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- NON-FUSED TRICYCLIC COMPOUNDS
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Provided herein are compounds and pharmaceutical compositions comprising said compounds that are useful for treating cancers. Specific cancers include those that are mediated by YAP/TAZ or those that are modulated by the interaction between YAP/TAZ and TEAD.
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Paragraph 00590; 00702
(2018/11/26)
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- Oxidative Coupling of Aromatic Amines and Nitrosoarenes: Iodine-Mediated Formation of Unsymmetrical Aromatic Azoxy Compounds
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I2/DABCO (iodine/1,4-diazabicyclo[2.2.2]octane)-mediated oxidative coupling of nitrosobenzenes with aromatic amines was revealed to lead to the production of unsymmetrical aromatic azoxy compounds, instead of azo compounds reported previously in Mills reaction. Our study illustrates that various aromatic amines can be efficiently coupled with nitrosobenzenes to produce unsymmetrical azoxy product, in which more than thirty unsymmetrical azoxybenzenes have been successfully prepared. The applicability to a broad range of substrates, scalability to large scales and mild reaction conditions make this new synthetic protocol very practical, providing a convenient and direct access to unsymmetrical azoxybenzenes. (Figure presented.).
- Yu, Xiaochun,Ding, Weijie,Ge, Panyu,Wang, Shun,Wang, Jichang
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supporting information
p. 3150 - 3156
(2018/08/24)
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- CHEMICAL COMPOUNDS AS INHIBITORS OF INTERLEUKIN-1 ACTIVITY
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The present disclosure relates to novel sulfonylurea and sulfonyl thiourea compounds and related compounds and their use in treating a disease or condition responsive to modulation of cytokines such as IL-1β and IL-18, modulation of NLRP3 or inhibition of the activation of NLRP3 or related components of the inflammatory process.
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Paragraph 00787; 00788
(2018/08/12)
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- Amine-mediated synthesis of amides from 1,3-dicarbonyl compounds through a domino diazo transfer/aminolysis process
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The dual role of amines as both catalysts and substrates for the synthesis of diazo compounds or carboxamides from 1,3-dicarbonyl compounds is described herein. In the presence of a suitable diazo transfer agent, primary and cyclic secondary amines act as basic catalysts for the diazo transfer reaction to malonates, β-keto esters, and β-diketones. Depending on the structure of the 1,3-dicarbonyl compound and the nucleophilicity of the amine, the resulting α-diazo-β-keto ester undergoes cleavage of the acyl group to give amides. A multifunctionalized γ-azido-α-diazo-β-keto ester was cleanly prepared in good yields by this one-pot protocol under practical and safe conditions, being employed in a Knoevenagel-type condensation with aromatic aldehydes to give densely functionalized diazo azido compounds. Further treatment of these unsaturated γ-azido-α-diazo-β-keto esters with primary amines readily furnished the corresponding α-azidocinnamamides in high yields, which were used in the synthesis of novel indole-2-carboxamides through the rhodium-catalyzed intramolecular C–H insertion.
- Costin, Taíssa A.,Dutra, Luiz G.,Bortoluzzi, Adailton J.,Sá, Marcus M.
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p. 4549 - 4559
(2017/07/11)
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- Difluoro methylation reagent, preparation method and application thereof (by machine translation)
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The present invention discloses a two-trifluoromethylation of the reagent, preparation method and application thereof. The invention [...] methylation reagent preparation process is simple, high yield; and the reagent can be a more moderate, high-efficiently the sulfonic acid, alcohol, carbonyl and on the α carbon atom of the difluoromethyl. (by machine translation)
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Paragraph 0116; 0117; 0118; 0119; 0120; 0121
(2017/10/23)
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- Rh(III)-Catalyzed Regio- and Chemoselective [4 + 1]-Annulation of Azoxy Compounds with Diazoesters for the Synthesis of 2H-Indazoles: Roles of the Azoxy Oxygen Atom
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A Rh(III)-catalyzed tandem C-H alkylation/intramolecular decarboxylative cyclization of azoxy compounds with diazoesters for the synthesis of 3-acyl-2H-indazoles is disclosed. The azoxy instead of the azo group enables a distinct approach for cyclative capture, leading to a [4 + 1]-annulation rather than a classic [4 + 2] manner. The azoxy oxygen atom is traceless after annulation, and further removal from the product is not required. This reaction features a complete regioselectivity for unsymmetrical azoxybenzenes and a compatibility of monoaryldiazene oxides.
- Long, Zhen,Wang, Zhigang,Zhou, Danni,Wan, Danyang,You, Jingsong
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supporting information
p. 2777 - 2780
(2017/06/07)
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- Rh-Catalyzed Regioselective ortho-C-H Carbenoid Insertion of Diarylazines
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The Rh-catalyzed ortho-C-H carbenoid insertion reaction of diarylazines with diazo compounds has been developed. A wide range of ortho-substituted diarylazines have been obtained in moderate to high yields with high regioselectivity at room temperature. The hydrolysis of the products could release ketones or aldehydes, giving access to aromatic 1,5-keto-diesters as valuable synthons for further chemical transformations.
- Yu, Yunliang,Kuai, Changsheng,Chauvin, Remi,Tian, Nian,Ma, Shuangshuang,Cui, Xiuling
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p. 8611 - 8616
(2017/08/23)
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- Divergent Reactivity of Thioalkynes in Lewis Acid Catalyzed Annulations with Donor–Acceptor Cyclopropanes
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Efficient methods for the convergent synthesis of (poly)cyclic scaffolds are urgently needed in synthetic and medicinal chemistry. Herein, we describe new annulation reactions of thioalkynes with phthalimide-substituted donor–acceptor cyclopropanes, which gave access to highly substituted cyclopentenes and polycyclic ring systems. With silyl-thioalkynes, the Lewis acid catalyzed [3+2] annulation reaction with donor–acceptor cyclopropanes took place to afford 1-thio-cyclopenten-3-amines. On the other hand, an unprecedented polycyclic compound was formed with alkyl-thioalkynes through a reaction pathway directly involving the phthalimide group. The two transformations proceeded in good yields and tolerated a large variety of functional groups.
- Racine, Sophie,Hegedüs, Bence,Scopelliti, Rosario,Waser, Jér?me
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supporting information
p. 11997 - 12001
(2016/08/16)
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- Highly Selective Ring Expansion of Bicyclo[3.1.0]hexenes
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A Ru-carbene-promoted ring expansion of bicyclo[3.1.0]hexenes with terminal alkynes is reported. The reaction delivers seven-membered carbocycles starting from readily available starting materials and was found to be highly regioselective. The resulting seven-membered ring products contain both conjugated diene and cyclopropane substructures that could be selectively reacted in subsequent transformations.
- Gratia, Synthia,Mosesohn, Kathryn,Diver, Steven T.
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supporting information
p. 5320 - 5323
(2016/11/02)
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- Cyclopropenation of internal alkynylsilanes and diazoacetates catalyzed by copper(i) N-heterocyclic carbene complexes
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Copper(i) N-heterocyclic carbene (CuNHC) complexes are more catalytically active than traditional transition metal salts for the cyclopropenation of internal alkynylsilanes and diazoacetate compounds. A series of 1,2,3-trisubstituted and 1,2,3,3-tetrasubstituted cyclopropenylsilane compounds were isolated in good overall yields. An interesting regioselective and chemodivergent reaction pathway was also observed to furnish a tetra-substituted furan for an electron-rich donor/acceptor diazoacetate. Finally, a practical synthesis of a cyclopropenyl-containing starting material that is useful for bioorthogonal chemistry is also described.
- Thomas, Thomas J.,Merritt, Benjamin A.,Lemma, Betsegaw E.,McKoy, Adina M.,Nguyen, Tri,Swenson, Andrew K.,Mills, Jeffrey L.,Coleman, Michael G.
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supporting information
p. 1742 - 1747
(2016/02/10)
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- C6-selective direct alkylation of pyridones with diazo compounds under Rh(III)-catalyzed mild conditions
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A Rh(III)-catalyzed highly efficient C6-alkylation of 2-pyridones has been achieved successfully with α-diazo carbonyl compounds. The developed method is simple, mild, and highly regioselective with a broad range of substrate scope. The regioselectivity is guided by the pyridyl substituent attached to the nitrogen center of the pyridone ring. The directing group can be easily removed, and the only formed byproduct is nitrogen. Furthermore, other similar heterocyclic scaffolds can also be functionalized regioselectively under the developed conditions.
- Das, Debapratim,Biswas, Aniruddha,Karmakar, Ujjwal,Chand, Santanu,Samanta, Rajarshi
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p. 842 - 848
(2016/02/18)
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- Copper-Catalyzed Regioselective Cascade Alkylation and Cyclocondensation of Quinoline N-Oxides with Diazo Esters: Direct Access to Conjugated π-Systems
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An inexpensive copper-catalyzed cascade regioselective alkylation, followed by cyclocondensation of quinoline N-oxides with α-diazo esters has been achieved successfully to provide heteroarene-containing conjugated π-systems. The developed method is simple, straightforward, and economical with a broad range of substrate scope. The dual role of copper catalyst in the C?H bond functionalization and in Lewis acid-promoted cyclization was explored.
- Biswas, Aniruddha,Karmakar, Ujjwal,Pal, Arun,Samanta, Rajarshi
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supporting information
p. 13826 - 13830
(2016/09/21)
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- Tetrahydro-1,3-oxazepines via Intramolecular Amination of Cyclopropylmethyl Cation
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An efficient synthesis of tetrahydro-1,3-oxazepines was developed involving the regioselective intramolecular amination of cyclopropylmethyl cation. The cation was generated by the abstraction of one imidate group in bis-imidate bearing a carbocation-stabilizing substituent. Using 1,1,2,3-tetrasubstituted cyclopropane substrates, highly diastereoselective intramolecular amination to trans-tetrahydro-1,3-oxazepines was achieved. The resulting tetrahydro-1,3-oxazepines were transformed to the homoallylamine derivatives in high yields.
- Skvorcova, Marija,Grigorjeva, Liene,Jirgensons, Aigars
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supporting information
p. 2902 - 2904
(2015/06/30)
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- Dichlorination of α-Diazo-β-dicarbonyls using (dichloroiodo)benzene
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Abstract α-Diazo-β-dicarbonyl compounds were chlorinated using (dichloro)iodobenzene and an activating catalyst. A broad range of reaction rates was observed, which paralleled the relative stability/nucleo-philicity of the diazo compounds. Acyclic diazocarbonyls reacted faster than cyclics, and β-diketones were much faster to react than β-keto esters or β-diesters. Lewis acid activation was used for the first time, allowing us to overcome instances of poor chemoselectivity. Though the yields ranged from low to good, this chlorination reaction has again proven a mild and effective halogenation strategy.
- Coffey, Keith E.,Murphy, Graham K.
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supporting information
p. 1003 - 1007
(2015/05/20)
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- Highly functionalized donor-acceptor cyclopropanes applied toward the synthesis of the Melodinus alkaloids
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Abstract A series of highly substituted vinylcyclopropanes were prepared and examined as reaction partners in a palladium-catalyzed (3+2) cycloaddition with nitrostyrenes. Described herein are our efforts to synthesize an elusive 1,1-divinylcyclopropane by several distinct approaches, and to apply surrogates of this fragment toward the synthesis of the Melodinus alkaloids.
- Goldberg, Alexander F.G.,Craig, Robert A.,O'Connor, Nicholas R.,Stoltz, Brian M.
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supporting information
p. 2983 - 2990
(2015/05/27)
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- Uncatalysed diaryldiazo cyclopropanations on bicyclic lactams: Access to annulated prolines
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The uncatalysed cycloaddition of substituted diaryldiazo compounds onto bicyclic unsaturated lactams derived from pyroglutamic acid efficiently leads to highly functionalised azatricyclononanes. The products are readily elaborated to deprotected pyroglutamate derivatives, providing rapid access to conformationally constrained amino acids and their analogues. Preliminary assessment of antibacterial activity against one Gram positive and one Gram negative organism indicated high levels of efficacy in some cases.
- Harris, Lawrence,Gilpin, Martin,Thompson, Amber L.,Cowley, Andrew R.,Moloney, Mark G.
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p. 6522 - 6550
(2015/06/16)
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- Synthesis of bicyclic tetrahydrofurans from linear precursors using manganese(III) acetate
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We have recently developed methodology based on oxidative radical reactions for the synthesis of [3.3.0]-bicyclic lactones containing both cyclopentanes and γ-lactams along with application of this methodology to the synthesis of natural products and complex molecular architectures. Herein we report an extension of this methodology to the synthesis of oxygen heterocycles including bicyclic bis-lactones.
- Chany, Anne-Caroline,Marx, Léo B.,Burton, Jonathan W.
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supporting information
p. 9190 - 9193
(2015/09/07)
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- Copper-catalyzed oxygen atom transfer of N-oxides leading to a facile deoxygenation procedure applicable to both heterocyclic and amine N-oxides
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Deoxygenation of various types of N-oxides including both heterocyclic and alkyl(aryl)amine derivatives has successfully been developed by the copper-catalyzed oxygen atom transfer using diazo compounds as the oxygen acceptor. The reaction proceeds smoothly over a broad range of substrates with excellent functional group tolerance under mild conditions. This journal is
- Jeong, Jisu,Lee, Donggun,Chang, Sukbok
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supporting information
p. 7035 - 7038
(2015/04/22)
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- Dynamic kinetic asymmetric [3 + 2] annulation reactions of aminocyclopropanes
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We report the first example of a dynamic kinetic asymmetric [3 + 2] annulation reaction of aminocyclopropanes with both enol ethers and aldehydes. Using a Cu catalyst and a commercially available bisoxazoline ligand, cyclopentyl- and tetrahydrofurylamines were obtained in 69-99% yield and up to a 98:2 enantiomeric ratio using the same reaction conditions. The method gives access to important enantio-enriched nitrogen building blocks for the synthesis of bioactive compounds.
- De Nanteuil, Florian,Serrano, Eloisa,Perrotta, Daniele,Waser, Jerome
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supporting information
p. 6239 - 6242
(2014/05/20)
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- Diazo transfer reaction to 1,3-dicarbonyl compounds with sulfonyl azides catalyzed by molecular sieves
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A simple and effective heterogeneous catalyst based on zeolite-type materials has been developed for the diazo transfer reaction involving 1,3-dicarbonyl compounds and tosyl azide. α-Diazo carbonyl compounds were obtained under mild conditions in good to high yields using commercial molecular sieve 4A or analogues as the catalyst. The best catalyst was found to be 4A-1000, a synthetic potassium-free nepheline obtained by heating molecular sieve 4A at 1000 C. Characterization of the resulting aluminosilicate by XRD, FTIR and SEM-EDS analysis confirmed the change of the crystal structure. Besides being nontoxic and inexpensive, the heterogeneous catalyst was readily removed by filtration and could be reused at least for four runs without any special treatment.
- Dutra, Luiz G.,Saibert, Cristine,Vicentini, Denice S.,Sá, Marcus M.
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