- 6-HETEROARYLOXY BENZIMIDAZOLES AND AZABENZIMIDAZOLES AS JAK2 INHIBITORS
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The present disclosure provides 6-heteroaryloxy benzimidazole and azabenzimidazole compounds and compositions thereof useful for inhibiting JAK2.
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Paragraph 0613-0614
(2021/11/13)
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- Formal Bromine Atom Transfer Radical Addition of Nonactivated Bromoalkanes Using Photoredox Gold Catalysis
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Organic transformations mediated by photoredox catalysis have been at the forefront of reaction discovery. Recently, it has been demonstrated that binuclear Au(I) bisphosphine complexes, such as [Au2(μ-dppm)2]X2, are capable of mediating electron transfer to nonactivated bromoalkanes for the generation of a variety of alkyl radicals. The transfer reactions of bromine, derived from nonactivated bromoalkanes, are largely unknown. Therefore, we propose that unique metal-based mechanistic pathways are at play, as this binuclear gold catalyst has been known to produce Au(III) Lewis acid intermediates. The scope and proposed mechanistic overview for the formal bromine atom transfer reaction of nonactivated bromoalkanes mediated by photoredox Au(I) catalysis is presented. The methodology presented afforded good yields and a broad scope which include examples using bromoalkanes and iodoarenes.
- Zidan, Montserrat,McCallum, Terry,Swann, Rowan,Barriault, Louis
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supporting information
p. 8401 - 8406
(2020/11/03)
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- Dimethyl malonate/LHMDS system as a new protocol for generating methyl formate anion (-COOMe) in the condensed-phase Dedicated to Professor Charles H. DePuy (1927-2013)
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The treatment of dimethyl malonate with LHMDS in anhydrous THF (condensed-phase) generates, in addition to the expected corresponding lithium enolate, methyl formate anion (or methoxycarbonyl anion, -COOMe) which can react with several electrophiles to give corresponding methoxycarbonyl derivatives by nucleophilic substitution reaction.
- Di Bussolo, Valeria,Princiotto, Salvatore,Martinelli, Elisa,Bordoni, Vittorio,Crotti, Paolo
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supporting information
p. 1644 - 1647
(2016/04/04)
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- Rhodium-Catalyzed Stereoselective Intramolecular [5 + 2] Cycloaddition of 3-Acyloxy 1,4-Enyne and Alkene
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The first rhodium-catalyzed intramolecular [5 + 2] cycloaddition of 3-acyloxy 1,4-enyne and alkene was developed. The cycloaddition is highly diastereoselective in most cases. Various cis-fused bicyclo[5.3.0]decadienes were prepared stereoselectively. The chirality in the propargylic ester starting materials could be transferred to the bicyclic products with high efficiency. Electron-deficient phosphine ligand greatly facilitated the cycloaddition. Up to three new stereogenic centers could be generated. The resulting diene in the products could be hydrolyzed to enones, which allowed the introduction of more functional groups to the seven-membered ring.
- Shu, Xing-Zhong,Schienebeck, Casi M.,Li, Xiaoxun,Zhou, Xin,Song, Wangze,Chen, Lianqing,Guzei, Ilia A.,Tang, Weiping
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supporting information
p. 5128 - 5131
(2015/11/03)
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- Chiral hetero- and carbocyclic compounds from the asymmetric hydrogenation of cyclic alkenes
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Several types of chiral hetero- and carbocyclic compounds have been synthesized by using the asymmetric hydrogenation of cyclic alkenes. N,P-Ligated iridium catalysts reduced six-membered cyclic alkenes with various substituents and heterofunctionality in good to excellent enantioselectivity, whereas the reduction of five-membered cyclic alkenes was generally less selective, giving modest enantiomeric excesses. The stereoselectivity of the hydrogenation depended more strongly on the substrate structure for the five- rather than the six-membered cyclic alkenes. The major enantiomer formed in the reduction of six-membered alkenes could be predicted from a selectivity model and isomeric alkenes had complementary enantioselectivity, giving opposite optical isomers upon hydrogenation. The utility of the reaction was demonstrated by using it as a key step in the preparation of chiral 1,3-cis-cyclohexane carboxylates. Copyright
- Verendel, J. Johan,Li, Jia-Qi,Quan, Xu,Peters, Byron,Zhou, Taigang,Gautun, Odd R.,Govender, Thavendran,Andersson, Pher G.
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supporting information; experimental part
p. 6507 - 6513
(2012/06/29)
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- Palladium-catalyzed oxidative aryltrifluoromethylation of activated alkenes at room temperature
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A palladium-catalyzed intramolecular oxidative aryltrifluoromethylation reaction of activated alkenes has been explored. The reaction allows for an efficient synthesis of a variety of CF3-containing oxindoles. Preliminary mechanistic study indicated that the reaction involves a Csp 3-PdIV(CF3) intermediate, which undergoes reductive elimination to afford a Csp3-CF3 bond.
- Mu, Xin,Wu, Tao,Wang, Hao-Yang,Guo, Yin-Long,Liu, Guosheng
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supporting information; experimental part
p. 878 - 881
(2012/02/17)
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- Iridium-catalyzed hydroiodination of functionalized alkynes
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The efficiency of an Ir(I)/HI system has been studied. The association of hydroiodic acid with iridium has been tested in the catalytic hydroiodination of alkynes. The use of [Ir(cod)Cl]2 dimer led to clean hydroiodination reactions and afforde
- Ez-Zoubir, Mehdi,Brown, Jack A.,Ratovelomanana-Vidal, Virginie,Michelet, Véronique
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experimental part
p. 433 - 441
(2011/02/16)
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- Rhi-catalyzed two-component [(5+2)+1] cycloaddition approach toward [5-8-5] ring systems
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Bringing it all together: [{Rh(CO)2Cl}2]-catalyzed two-component [(5+2)+1] cycloaddition of ene-vinylcyclopropanes with various tether types and substituents with CO has been designed for the one-pot synthesis of fused tricyclic cyclooctenones with atom and step economies.
- Huang, Feng,Yao, Zhong-Ke,Wang, Yi,Wang, Yuanyuan,Zhang, Jialing,Yu, Zhi-Xiang
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supporting information; experimental part
p. 1555 - 1559
(2011/08/05)
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- USE IN PERFUMERY AND FLAVORING AND PROCESS FOR THE PREPARATION OF 5,5-DIMETHYL-3-ETHYL-3,4-DIHYDROFURAN-2-ONE
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The invention relates to the use of 5,5-dimethyl-3-ethyl-3,4-dihydrofuran-2-one (A), named “Noxolide” by the applicant, as an olfactory agent in perfumery, and also as a food flavouring. The invention also relates to a novel process for the preparation of 5,5-dimethyl-3-ethyl-3,4-dihydrofuran-2-one.
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Page/Page column 2
(2010/05/13)
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- Synthesis of small and large fused bicyclic compounds by tandem dienyne ring-closing metathesis
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(Equation Presented). A tandem ring-closing metathesis reaction using ruthenium catalyst was carried out to synthesize various fused bicyclic compounds containing both small and large rings. Fast ring-closure of the small ring and slow ring-closure of the large ring resulted in the formation of only one isomer. Further manipulation such as the Diels-Alder reaction was carried out to prepare a complex molecule containing multiple rings of different sizes.
- Park, Hyeon,Hong, You-Lee,Kim, Yongjoo B.,Choi, Tae-Lim
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supporting information; experimental part
p. 3442 - 3445
(2010/10/01)
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- Enantioselective, organocatalyzed, intramolecular aldol lactonizations with keto acids leading to Bi- and Tricyclic β-lactones and topology-morphing transformations
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Quickly emerging complexity characterizes the asymmetric, nucleophile-catalyzed aldol lactonization (NCAL) process with keto acid substrates and subsequent topology-altering reactions. The utility of chiral cyclic isothiourea catalysts as nucleophilic pro
- Leverett, Carolyn A.,Purohit, Vikram C.,Romo, Daniel
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supporting information; experimental part
p. 9479 - 9483
(2011/02/22)
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- Palladium-catalyzed desulfinylative C-C allylation of Grignard reagents and enolates using allylsulfonyl chlorides and esters
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2-Methylprop-2-ene-, prop-2-ene-, 1-methylprop-2-ene-, and (E)-but-2-enesulfonyl chlorides have been used as electrophilic partners in desulfinylative palladium-catalyzed C-C coupling with Grignard reagents and sodium salts of dimethyl malonate and methyl
- Rao Volla, Chandra M.,Dubbaka, Srinivas Reddy,Vogel, Pierre
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experimental part
p. 504 - 511
(2009/04/07)
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- Features and applications of [Rh(CO)2Cl]2-catalyzed alkylations of unsymmetrical allylic substrates
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(Chemical Equation Presented) A novel regio- and stereoselective [Rh(CO)2Cl]2-catalyzed allylic alkylation of unsymmetrical allylic carbonates was discovered. The regioselectivity of the reaction favors product ratios in which substitution occurs at the carbon bearing the leaving group. When an enantiomerically enriched carbonate (≥99% ee) was examined, the Rh(I)-catalyzed allylic alkylation proceeded stereoselectively to provide the alkylation product with retention of absolute stereochemistry (98% ee). To establish the scope of the [Rh(CO)2Cl]2-catalyzed allylic alkylation, a variety of carbon and heteroatom nucleophiles were examined and the results described. As an application of the Rh(I)-catalyzed allylic alkylation, a series of novel domino reactions have been developed that couple the unique regio- and stereoselective [Rh(CO)2Cl]2- catalyzed alkylation of allylic trifluoroacetates with an intramolecular Pauson-Khand annulation, a cycloisomerization, or a [5+2] cycloaddition. A unique aspect of the method described is the use of a single catalyst to effect sequential transformations in which the catalytic activity is moderated simply by controlling the reaction temperature. Implementation of such processes provides a rapid and efficient entry to a variety of bicyclic carbon skeletons from simple precursors.
- Ashfeld, Brandon L.,Miller, Kenneth A.,Smith, Anna J.,Tran, Kristy,Martin, Stephen F.
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p. 9018 - 9031
(2008/03/13)
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- Intramolecular additions of alcohols and carboxylic acids to inert olefins catalyzed by silver(I) triflate
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(Chemical Equation Presented) Intramolecular additions of hydroxyl or carboxyl groups to inert olefins catalyzed by simple silver(I) triflate are described. Good to excellent yields can be obtained for a range of substrates under relatively mild conditions. This reaction represents one of the simplest methods to construct cyclic ethers or lactones.
- Yang, Cai-Guang,Reich, Nicholas W.,Shi, Zhangjie,He, Chuan
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p. 4553 - 4556
(2007/10/03)
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- Sulfur-mediated radical cyclisation reactions on solid support
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Two methods for effecting radical cyclisation reactions of solid-supported 1,6-dienes are described. Additions of thiophenol and p-tolyl benzeneselenosulfonate have each been achieved with a concomitant 5-exo-trig radical cyclisation leading to the formation of highly functionalised cyclopentanes.
- Harrowven, David C.,May, Peter J.,Bradley, Mark
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p. 503 - 506
(2007/10/03)
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- Unexpected remarkable stability of primary ozonides derived from alkenyl stannanes. One-pot synthesis of 1,2-diols from alkynes
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(Matrix Presented) Primary ozonides derived from alkenyl stannanes display an unusual stability and can be transformed into 1,2-diols by treatment with dimethyl sulfide and borane-methyl sulfide complex. This observation has been incorporated into the development of a novel one-pot strategy for the conversion of alkynes into 1,2-diols.
- Gomez, Ana M.,Company, Maria D.,Valverde, Serafin,Lopez, J. Cristobal
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p. 383 - 386
(2007/10/03)
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- Radical-chain addition of aldehydes to alkenes catalysed by thiols
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Thiols catalyse the radical-chain addition of primary aliphatic aldehydes R1CH2CHO to terminal alkenes H2C=CR2R3 to give ketonic adducts R1CH2C(O)CH2C(H)R2R3 in moderate to good yields.The reaction takes place under mild conditions (dioxane solvent, 60 deg C) and is initiated by di-tert-butyl hyponitrite (TBHN).Thiol catalysis is effective for hydroacylation of electron-rich, -neutral and -deficient alkenes, but is most efficient for addition to electron-rich double bonds.For example, the addition of butanal (2 equiv.) to isopropenyl acetate in the presence of TBHN (2x2.5 molpercent) and methyl thioglycolate (MeO2CCH2SH; 2x5 molpercent) gives the adduct in 80percent yield, whilst a similar reaction in the absence of thiol catalyst affords only an 8percent yield.Other enol acetates, silyl enol ethers, an enol phosphate and butyl vinyl ether react similarly.For comparison, the reaction of butanoyl phenyl selenide with isopropenyl acetate, in the presence of tributyltin hydride and azoisobutyronitrile initiator in benzene at 80 deg C, gives the adduct in only 7percent yield.Methyl thioglycolate is generally the most efficient catalyst for hydroacylation of electron-rich alkenes, whilst tert-dodecanethiol is more effective for addition of aldehydes to electron-deficient alkenes.Triorganosilanethiols also function as catalysts, as does the arenethiol 2,4,6-tris(trifluoromethyl)thiophenol.The role of the thiol is to act as a polarity-reversal catalyst that promotes the overall hydrogen-atom transfer from the aldehyde to the carbon-centred radical produced by addition of the acyl radical to the alkene.Intramolecular hydroacylation is also subject to thiol catalysis and the radical-chain cyclisation of citronellal to a mixture of menthone and isomenthone is effectively promoted in the presence of triphenylsilanethiol.
- Dang, Hai-Shan,Roberts, Brian P.
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- Regioselective palladium-catalysed coupling reactions of vinyl chlorides with carbon nucleophiles
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Vinyl chlorides bearing methyl groups in the 2-position can be activated catalytically by palladium(0)-complexes of 1,4-bis(dicyclohexylphosphino)butane, the process involving vinyl-allyl isomerization via CH-activation followed by nucleophilic attack of
- Reetz, Manfred T.,Wanninger, Klaus,Hermes, Marcus
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p. 535 - 536
(2007/10/03)
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- Bis(aminophosphine)-nickel complexes as efficient catalysts for alkylation of allylic acetates with stabilized nucleophiles
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The alkylation of a variety of allylic acetates with dimethyl malonate catalysed by nickel-diphosphine complexes is reported. It is shown that in most cases bis(aminophosphine) type ligands lead to much more efficient catalysts than dppb and other usual d
- Bricout, Herve,Carpentier, Jean-Francois,Mortreux, Andre
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p. 6105 - 6108
(2007/10/03)
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- (Phenylsulfonyl)allenes as substrates for cycloaddition reactions: Intramolecular cyclizations onto unactivated alkenes
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The reaction of a series of allyl-substituted bis(phenylsulfonyl)methanes or dimethyl malonates with 2,3-bis(phenylsulfonyl)-1,3-butadiene in the presence of base afforded alkenyl-substituted allenes in good yield. The reaction proceeds by initial attack of the soft carbanion onto the terminal position of the diene, and this is followed by PhSO2- elimination to give the phenylsulfonyl-substituted allene. Themal [2 + 2]-cycloaddition proceeded across the C1-C2 double bond of the allene with completely sterospecificity. Stepwise bonding prefers to occur in a 1,6-exo manner rather than in a 1,7-endo fashion. Substitution at the 7-position of the π-bond causes a crossover in the regioselectivity of the [2 + 2]-cycloaddition process. All products can be rationalized by a mechanism which includes an initial carbon-carbon bond formation involving the central allene carbon to give a diradical intermediate. The product distribution is then determined by the substitution pattern of the alkene and the fate of the diradical intermediate.
- Padwa, Albert,Meske, Michael,Murphree, S. Shaun,Watterson, Scott H.,Ni, Zhijie
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p. 7071 - 7080
(2007/10/02)
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- Palladium assisted alkylation-insertion reactions of chiral ene-carbamates
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Palladium(II) complexes of chiral ene-carbamate 2 underwent efficient, stereoselective alkylation by malonate carbanions having pendent unsaturated side chains. The resulting σ-alkylpalladium(II) complexes underwent efficient insertion of carbon monoxide to produce esters. Insertion of the pendent unsaturated groups was less efficient, and led to mixtures of insertion products with little stereoselectivity.
- Laidig,Hegedus
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p. 527 - 532
(2007/10/02)
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- Novel aminopimelic acids
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A) Compounds selected from the group consisting of a compound of the formula STR1 wherein U is STR2 m and n are individually 1 or 2 of one, the dotted lines is a single double bond optionally of cis or trans configuration, a is selected from the group consisting of hydrogen, methyl and methylene, Y is selected from the group consisting of hydrogen, residue of an amino acid with an α-or ω-carboxyl and a peptide or 2,3 or 4 amino acids with the amine optionally acylated with an optionally unsaturated aliphatic carboxylic acid of 6 to 24 carbon atoms or alkylated with alkyl of 1 to 8 carbon atoms, R is selected from the group consisting of hydrogen, alkyl of 1 to 8 carbon, alkenyl and alkynyl of 2 to 8 carbon atoms optionally substituted with at least one halogen with the proviso that if Y is hydrogen, alanine or proline and if a is hydrogen, U contains a double bond; and B) their non-toxic, pharmaceutically acceptable salts with bases or acids, the alkyl esters of 1 to 6 carbon atoms and their primary and secondary amides having remarkable immunomodulatric properties and anti-bacterial activity.
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- Intramolecular Reactions of N-Nitrenes: Description of the Transition State Geometry for Addition to Alkenes
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Oxidation of the N-aminoquinazolones (10) and (11) generates the corresponding N-nitrenes which add intramolecularly to both double bonds.Although nitrene addition is stereospecifically cis, both faces of each double bond are attacked and consequently stereoisomers are formed.From the different selectivity of the N-nitrenes for the two double bonds in (10) and (11) by comparison with (15) and (24), respectively, and from a consideration of the stereoisomer ratios, it is concluded that concerted addition of the N-nitrene to the double bonds in (10) and (11) obtains via a transition-state geometry resembling that shown in (34).
- Atkinson, Robert S.,Grimshire, Michael J.
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p. 1135 - 1146
(2007/10/02)
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