- INHIBITORS OF NOROVIRUS AND CORONAVIRUS REPLICATION
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Compounds of Formula (I) and methods of inhibiting the replication of viruses in a biological sample or patient, of reducing the amount of viruses in a biological sample or patient, and of treating a virus infection in a patient, comprising administering to said biological sample or patient an effective amount of a compound represented by Formula (I), a compound of Table A or B or a pharmaceutically acceptable salt thereof.
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Paragraph 002112-002114
(2021/10/15)
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- Synergistic Relay Reactions To Achieve Redox-Neutral α-Alkylations of Olefinic Alcohols with Ruthenium(II) Catalysis
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Herein, we report a ruthenium-catalyzed redox-neutral α-alkylation of unsaturated alcohols based on a synergistic relay process involving olefin isomerization (chain walking) and umpolung hydrazone addition, which takes advantage of the interaction between the two rather inefficient individual reaction steps to enable an efficient overall process. This transformation shows the compatibility of hydrazone-type “carbanions” and active protons in a one-pot reaction, and at the same time achieves the first Grignard-type nucleophilic addition using olefinic alcohols as latent carbonyl groups, providing a higher yield of the corresponding secondary alcohol than the classical hydrazone addition to aldehydes does. A broad scope of unsaturated alcohols and hydrazones, including some complex structures, can be successfully employed in this reaction, which shows the versatility of this approach and its suitability as an alternative, efficient means for the generation of secondary and tertiary alcohols.
- Kan, Jian,Li, Chao-Jun,Li, Chen-Chen,Li, Jianbin,Lv, Leiyang,Qiu, Zihang
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supporting information
p. 4544 - 4549
(2020/02/04)
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- Photocatalytic carbanion generation-benzylation of aliphatic aldehydes to secondary alcohols
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We present a redox-neutral method for the photocatalytic generation of carbanions. Benzylic carboxylates are photooxidized by single electron transfer; immediate CO2 extrusion and reduction of the in situ formed radical yields a carbanion capable of reacting with aliphatic aldehydes as electrophiles giving the Grignard analogous reaction product.
- Donabauer, Karsten,Maity, Mitasree,Berger, Anna Lucia,Huff, Gregory S.,Crespi, Stefano,K?nig, Burkhard
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p. 5162 - 5166
(2019/06/05)
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- Unusual traits of cis and trans-2,3-dibromo-1,1-dimethylindane on the way from 1,1-dimethylindene to 2-bromo-, 3-bromo-, and 2,3-dibromo-1,1-dimethylindene
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Do not rely on the widely accepted rule that vicinal, sp3-positioned protons in cyclopentene moieties should always have more positive 3J NMR coupling constants for the cis than for the trans arrangement: Unrecognized exceptions might misguide one to wrong stereochemical assignments and thence to erroneous mechanistic conclusions. We show here that two structurally innocent-looking 2,3-dibromo-1,1-dimethylindanes violate the rule by means of their values of 3J(cis) = 6.1 Hz and 3J(trans) = 8.4 Hz. The stereoselective formation of the trans diastereomer from 1,1-dimethylindene was improved with the tribromide anion (Br3-) as the brominating agent in place of elemental bromine; the ensuing, regiospecific HBr elimination afforded 3-bromo-1,1-dimethylindene. The addition of elemental bromine to the latter compound, followed by thermal HBr elimination, furnished 2,3-dibromo-1,1-dimethylindene, whose Br/Li interchange reaction, precipitation, and subsequent protolysis yielded only 2-bromo-1,1-dimethylindene.
- Knorr, Rudolf,Stephenson, David S.,Lattke, Ernst,B?hrer, Petra,Ruhdorfer, Jakob
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supporting information
p. 1178 - 1184
(2016/07/06)
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- A General, Practical Triethylborane-Catalyzed Reduction of Carbonyl Functions to Alcohols
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A combination of the abundant and low-cost triethylborane and sodium alkoxide generates a highly efficient catalyst for reduction of esters, as well as ketones and aldehydes, to alcohols using an inexpensive hydrosilane under mild conditions. The catalyst system exhibits excellent chemoselectivity and a high level of functional group tolerance. Mechanistic studies revealed a resting state of sodium triethylalkoxylborate that is the product of the reaction of BEt3 with sodium alkoxide. This borate species reacts with hydrosilane to form NaBEt3H, which rapidly reduces esters.
- Peng, Dongjie,Zhang, Mintao,Huang, Zheng
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supporting information
p. 14737 - 14741
(2015/10/19)
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- Examining the origin of selectivity in the reaction of racemic alcohols with chiral N-phosphoryl oxazolidinones
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A range of known and novel N-phosphoryl oxazolidinones and imidazolidinones were prepared and screened in the kinetic resolution of a range of racemic magnesium chloroalkoxides. Models are proposed to account for the enantioselectivity achieved based on a combination of chiral relay effects, generation of transient stereochemistry and the structure of the intermediate magnesium alkoxide.
- Crook, Samuel,Parr, Nigel J.,Simmons, Jonathan,Jones, Simon
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p. 1298 - 1308
(2015/01/09)
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- Synthesis of Chiral 3-Alkyl-3,4-dihydroisocoumarins by dynamic kinetic resolutions catalyzed by a Baeyer-Villiger Monooxygenase
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"Chemical Equation Presented" Baeyer-Villiger monooxygenases have been tested, in the oxidation of racemic benzofused ketones. When employing a single mutant of phenylacetone monooxygenase (M.446G PAMO) under the proper reaction conditions, it was possible to achieve 3-substituted 3,4-dihydroisocoumarins with, high yields and optical purities through regioselective dynamic kinetic resolution processes.
- Rioz-Martinez, Ana,De Gonzalo,Torres Pazmino, Daniel E.,Fraaije, Marco-W.,Gotor, Vicente
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supporting information; experimental part
p. 2073 - 2076
(2010/06/17)
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- Generation of allylic and benzylic organolithium compounds by fluorine-lithium exchange: Reaction with electrophiles
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The application of the naphthalene-catalysed lithiation methodology to allylic and benzylic fluorides 1 led to the corresponding allylic and benzylic organolithium reagents, which, in the presence of different electrophiles (Barbier-type reaction conditions), afforded the expected products 2 in moderate yields. The procedure was useful for the transformation of primary, secondary and tertiary benzylic fluorides into the corresponding lithium derivatives. When a two-step lithiation process was used (treatment of fluoride 1 with lithium and a catalytic amount of naphthalene, followed by addition of the electrophilic reagent), only Wurtz-type coupling products were formed.
- Guijarro, David,Yus, Miguel
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- Generation of allylic and benzylic organolithium reagents from the corresponding ester, amide, carbonate, carbamate and urea derivatives
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The reaction of different allylic and benzylic non-enolisable esters or amides (1), carbonates (4), carbamates (6, 7) and ureas (8) with an excess of lithium powder and a catalytic amount of naphthalene (10%) in the presence of an electrophile [(i)PrCHO, (t)BuCHO, PhCHO, Me2CO, Et2CO, (CH2)5CO, Ph2CO, Me3SiCl] in THF at different temperatures (-78, -30 or 0°C) leads, after hydrolysis with water to the corresponding allylated or benzylated products (2).
- Alonso, Emma,Guijarro, David,Martinez, Pedro,Ramon, Diego J.,Yus, Miguel
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p. 11027 - 11038
(2007/10/03)
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- Arene-catalysed lithiation of triflates and triflamides under Barbier-type conditions: An indirect transformation of alcohols and amines into organolithium compounds
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The reaction of alkyl triflates 1 or benzyl triflamides 3 with an excess of lithium powder and a catalytic amount of naphthalene (4 mol%) in the presence of different electrophiles [Me3SiCl, Pr(i)CHO, Bu(t)CHO, PhCHO, 4-MeOC6H4-CHO, CH3(CH2)6CHO, Et2CO, (CH2)5CO, (c-C3H5)2CO, PhCOMe, 4-MeC6H4COPh, PhCh=NPh, n-C8H7CON(CH2)4] in THF at temperature ranging between -78 and 0°C leads, after hydrolysis with water, to the corresponding condensation products 2. When α,β-unsaturated carbonyl compounds are used as electrophilic compounds 1,2- (3-cyclohexenone) or 1,4-addition (cinnamaldehyde or benzylideneacetone) takes place depending on the electrophile used.
- Alonso, Emma,Ramon, Diego J.,Yus, Miguel
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p. 14341 - 14348
(2007/10/03)
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- Intramolecular meta photocycloaddition of conformationally restrained 5-phenylpent-1-enes. Part II: Steric and electronic effects caused by 4-mono- and 4-disubstitution
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The meta photocycloaddition of 4-substituted 5-phenylpent-1-enes. 10-18, has been studied. The monosubstituted derivatives always prefer 2,6 addition, independent of the size of the substituent. For 2,6 addition two basic conformations are possible. Disubstituted compounds yield predominantly 1,3 addition with the sterically more demanding group exo. Except for the methoxymethyl and THF derivative the oxygen is found exo as a result of repulsion, while the monohydroxy derivative gives also endo which might be explained by hydrogen bonding. The products from compound 11 change from mainly endo-OH in cyclohexane to chiefly exo-OH in methanol. Much similarity is found with Diels-Alder cycloaddition.
- Barentsen, Helma M.,Sieval, Alex B.,Cornelisse, Jan
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p. 7495 - 7520
(2007/10/02)
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- Arene-catalysed reductive desulfonylation and desulfinylation reactions: New routes for alkyllithiums
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The reactions of alkyl phenyl sulfones (1) with an excess of lithium powder and a catalytic amount of naphthalene (8 mol %) in the presence of a carbonyl compound or chlorotrimethylsilane (Barbier-type conditions) in THF at temperatures ranging between -78 and 20°C leads, after hydrolysis, to the expected products (2) arising from the corresponding alkyllithium generated in situ. When the same methodology is applied to sulfolene (3) or different alkyl phenyl sulfoxides (6), cyclic sulfinates 5 or products 2 are, respectively, obtained, the yields being, in general modest.
- Alonso, Emma,Guijarro, David,Yus, Miguel
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p. 2699 - 2708
(2007/10/02)
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- Direct Transformation of Trialkyl Phosphates into Organolithium Compounds by a DTBB-Catalysed Lithiation
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The reaction of different alkylic or phenylic phosphates 1 with an excess of lithium powder and a catalytic amount of DTBB (5 mol percent) in the presence of an electrophile -Barbier-type reaction conditions- in THF at -30 deg C leads to the formation of the expected products 2, resulting from the reaction of the in situ generated organolithium compound with the corresponding electrophile.
- Guijarro, David,Mancheno, Balbino,Yus, Miguel
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p. 8551 - 8558
(2007/10/02)
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- Naphthalene-Catalysed Reductive Desulfonylation with Lithium: Alkyllithiums from Alkyl Phenyl Sulfones
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The reaction of alkyl aryl sulfones 1 with an excess of lithium powder and a catalytic amount of naphthalene (8 mol percent) in the presence of a carbonyl compound iCHO, PhCHO, Et2CO, (CH2)5CO> or trimethylchlorosilane (Barbier-type conditions) in THF at temperatures ranging between -78 and 20 deg C leads, after hydrolysis with water, to the expected coupling products, arising from the corresponding alkyllithium in situ generated, in 30-61percent yields.
- Guijaro, David,Yus, Miguel
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p. 2965 - 2968
(2007/10/02)
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- Organolithium reagents by reductive decyanation of nitriles with lithium and a catalytic amount of 4,4'-di-tert-butyl-biphenyl in a Barbier-type reaction
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The reaction of different nitriles 1 with an excess of lithium powder (1:14 molar ratio) and a catalytic amount of 4,4'-di-tert-butylbiphenyl (5 mol %) in the presence of a carbonyl compound (Barbier-type conditions) in THF at low temperature (-30 or -78°C) leads to the corresponding compounds 2 resulting from the coupling between the electrophile and the organolithium intermediate arising from a reductive decyanation of the starting nitrile 1. This new reaction can be also applied to the use of trimethylchlorosilane as electrophile at 0°C.
- Guijarro,Yus
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p. 3447 - 3452
(2007/10/02)
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- Naphthalene-Catalysed Lithiation of Allylic and Benzylic Mesylates: A New Method for Allyl, Methallyl, and Benzyl Lithium
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The reaction of allylic or benzylic mesylates (1) with an excess of lithium powder and a catalytic amount of naphthalene (4 mol percent) in THF at -78 deg C leads to a solution of the corresponding organolithium derivatives, which by treatment with different electrophiles yield the expected products 2-7.As an alternative route, the process can be carried out at 0 deg C by adding the corresponding mesylate together with the electrophile to a suspension of the activated lithium in THF, in a Barbier-type reaction.
- Guijarro, D.,Mancheno, B.,Yus, M.
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p. 4593 - 4600
(2007/10/02)
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- The Autoxidation of 1-Phenylalk-1-ynes. Proof of Oxirenes as Intermediates in the Oxidation of Acetylenes
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In the autoxidations of 1-phenylprop-1-yne, 1-phenylbut-1-yne, and 1-phenyl-3-methylbut-1-yne a considerable attack at the CC triple bond takes place.Both products of the oxidative cleavage of the CC bond and products formed through the corresponding oxirenes were detected.The oxirenes rearrange via the isomeric ketocarbenes to ketenes, which yield the corresponding carboxylic acids or their esters.A part of the intermediate ketenes is oxidized with decarboxylation to lower ketones.All products were identified and quantitatively determined after LiAlH4 reduction to the corresponding alcohols.
- Dao, Le Thi Anh,Blau, Karla,Pritzkow, Wilhelm,Schmidt-Renner, Wolfgang,Voerckel, Volkmar,Willecke, Lothar
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- PHOTOSUBSTITUTION OF BENZYL HYDROGENS WITH ALCOHOLIC MOIETIES. SELECTIVE FORMATION OF ALKYLBENZENE CARBINOLS
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Irradiations of alkylbenzene compounds with various alcohols in an air atmosphere, resulted in substitution of the benzyl hydrogens with alcoholic moieties in a very selective mode.
- Pasternak, Mordechai,Morduchowitz, Abraham
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p. 3439 - 3442
(2007/10/02)
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- Medium-ring Ketone Synthesis. Intramolecular Acylation of Sulfur-stabilized Carbanions: A Model Study
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Intramolecular acylation of the sulfur-stabilized carbanions of the acyclic ester 9 and amide sulfides 11 was carried out as a model study for developing an effective method for the construction of medium-ring ketones by ring closure.Reaction of 9a-c or 11a-g with lithium diisopropylamide (LDA) proceeded smoothly and the expected keto sulfides 10a-c or 12a-g, respectively, were obtained.In the cases where R1 and/or R2 in 11 were normal alkyl groups, the reaction did not take place.However, these difficulties were readily overcome either by introducing a methyl group next to the carbonyl group or by converting the sulfides into the corresponding sulfoxides or sulfones.Acylation in the allyl sulfides 11b, d, f and the allyl sulfone 20b takes place at the α-position to the sulfur atom, yielding β,γ-unsaturated ketones.A reductive removal of the sulfide moiety or its conversion into other functional groups was also examined.
- Ohtsuka, Yasuo,Oishi, Takeshi
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p. 443 - 453
(2007/10/02)
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- SOME ORGANIC REACTIONS PROMOTED BY SAMARIUM DIIODIDE
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Various homoallylic alcohols and homobenzylic alcohols were prepared by the reaction between aldehydes and allylic or benzylic halides in the presence of samarium diiodide.This iodide is also a very good reagent for formation of pinacols from aldehydes or ketones.The reactions are especially fast and selective in the case of substituted benzaldehydes.The reactivities of various nitrogen functional groups (imine, oxime, nitro, azo, cyano) towards SmI2 were also examined.
- Souppe, J.,Danon, L.,Namy, J.L.,Kagan, H.B.
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p. 227 - 236
(2007/10/02)
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- Synthese de methoxycarbonylindenes, dihydro-1,2 naphtalenes et benzocycloheptene. Obtention des indanones-1, des tetralones-1 et de la benzosuberone correspondantes
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The synthesis of methoxycarbonylindenes, 1,2-dihydro-naphtalenes, and benzocycloheptene starting from the corresponding 1-indanones, 1-tetralones, and benzosuberone is reported.The starting ketones were synthesized by methods described in the literature which were optimized; in some cases new processes are described.
- Verbel, Joel,Carrie, Robert
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p. 116 - 124
(2007/10/02)
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- SAMARIUM DIIODIDE AS COUPLING AGENT BETWEEN ALDEHYDES AND ORGANIC HALIDES FOR THE SYNTHESIS OF HOMOALLYLIC AND HOMOBENZYLIC ALCOHOLS
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Many aliphatic aldehydes are transformed into secondary alcohols by reaction with allyl halides or benzylic halides in presence of SmI2
- Souppe, J.,Namy, J. L.,Kagan, H. B.
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p. 3497 - 3500
(2007/10/02)
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- A ONE POT SYNTHESIS OF UNSYMMETRICAL SECONDARY ALCOHOLS FROM TWO GRIGNARD REAGENTS
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The sequential addition of two Grignard reagents to 2-(N-methyl-N-formyl)-amino-pyridine in tetrahydrofuran provides a high yield one pot synthesis of unsymmetrical secondary alcohols.
- Comins, Daniel L.,Dernell, William
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p. 1085 - 1088
(2007/10/02)
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