- Dual H-bond activation of NHC-Au(i)-Cl complexes with amide functionalized side-arms assisted by H-bond donor substrates or acid additives
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Novel approach with amide-tethered H-bond donor NHC ligands enabled Au(i)-catalysis via H-bonding. The plain NHC-Au(i)-Cl complex catalysed conversions of terminal N-propynamides to oxazolines, and enyne cycloisomerization with an acid additive, in DCM at
- Sepp?nen, Otto,Aikonen, Santeri,Muuronen, Mikko,Alamillo-Ferrer, Carla,Burés, Jordi,Helaja, Juho
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supporting information
p. 14697 - 14700
(2020/12/02)
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- Chemoselective Synthesis of α-Amino-α-cyanophosphonates by Reductive Gem-Cyanation-Phosphonylation of Secondary Amides
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A novel approach to α-amino-α-cyanophosphonates has been developed. The method features a Tf2O-mediated reductive geminal cyanation/phosphonylation of secondary amides. Mild reaction conditions, high bond-forming efficiency, inexpensive readily available starting materials, and good to excellent yields with wide functional group compatibility constitute the main advantages of this method. The protocol can be run on a gram scale.
- Chen, Ting-Ting,Wang, Ai-E,Huang, Pei-Qiang
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supporting information
p. 3808 - 3812
(2019/05/24)
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- Formamides as Lewis Base Catalysts in SNReactions—Efficient Transformation of Alcohols into Chlorides, Amines, and Ethers
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A simple formamide catalyst facilitates the efficient transformation of alcohols into alkyl chlorides with benzoyl chloride as the sole reagent. These nucleophilic substitutions proceed through iminium-activated alcohols as intermediates. The novel method, which can be even performed under solvent-free conditions, is distinguished by an excellent functional group tolerance, scalability (>100 g) and waste-balance (E-factor down to 2). Chiral substrates are converted with excellent levels of stereochemical inversion (99 %→≥95 % ee). In a practical one-pot procedure, the primary formed chlorides can be further transformed into amines, azides, ethers, sulfides, and nitriles. The value of the method was demonstrated in straightforward syntheses of the drugs rac-Clopidogrel and S-Fendiline.
- Huy, Peter H.,Motsch, Sebastian,Kappler, Sarah M.
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p. 10145 - 10149
(2016/08/16)
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- METHOD OF CONVERTING ALCOHOL TO HALIDE
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The present invention relates to a method of converting an alcohol into a corresponding halide. This method comprises reacting the alcohol with an optionally substituted aromatic carboxylic acid halide in presence of an N-substituted formamide to replace a hydroxyl group of the alcohol by a halogen atom. The present invention also relates to a method of converting an alcohol into a corresponding substitution product. The second method comprises: (a) performing the method of the invention of converting an alcohol into the corresponding halide; and (b) reacting the corresponding halide with a nucleophile to convert the halide into the nucleophilic substitution product.
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Page/Page column 51; 172; 175
(2017/01/02)
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- Sulfonimidation via ring-opening of 2-oxazolines with acidic sulfonimide nucleophiles
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Acidic sulfonimide nucleophiles including dibenzenesulfonimide, o-benzenesulfonimide, dimethanesulfonimide, and N-(methylsulfonyl)-benzenesulfonamide are discovered to open a variety of alkyl-, aryl- and heteroaryl-2-oxazoline rings to provide the sulfonimidation products in refluxing 1,4-dioxane. The electron-rich 2-oxazoline substrates worked well for the nucleophilic ring-opening reactions while no reaction took place for the electron-poor 2-oxazoline substrates.
- Gutierrez, David A.,Dean, Dayton R.,Laxamana, Candace M.,Migliozzi-Smith, Madyson,O'Brien, Connor J.,O'Neill, Claire L.,Li, Jie Jack
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p. 261 - 276
(2016/07/06)
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- One-pot triflic anhydride-mediated synthesis of 1,2-disubstituted 2-imidazolines from N-(2-haloethyl)amides and amines
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A one-pot synthesis of 1,2-disubstituted 2-imidazolines from N-(2-haloethyl)amides has been developed. The reaction affords high yields of diverse 1,2-disubstituted 2-imidazolines from triflic anhydride-mediated dehydration of amides followed by installat
- Ellsworth, Alyssa A.,Magyar, Christina L.,Hubbell, Grace E.,Theisen, Chelsea C.,Holmes, Daniel,Mosey, R. Adam
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p. 6380 - 6389
(2016/09/23)
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- NHC-amide donor ligands in rhodium complexes: Syntheses and characterisation
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Rhodium(I) complexes bearing amide-functionalised NHC ligands were synthesized in high yields through various synthetic routes and from different metal precursors, showing the versatility of such systems. By changing the ancillary ligands on the rhodium f
- Warsink, Stefan,Venter, Johan A.,Roodt, Andreas
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p. 195 - 201
(2015/02/19)
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- Copper-catalyzed oxidative amidation of aldehydes with amine salts: Synthesis of primary, secondary, and tertiary amides
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A practical method for the amidation of aldehydes with economic ammonium chloride or amine hydrochloride salts has been developed for the synthesis of a wide variety of amides by using inexpensive copper sulfate or copper(I) oxide as a catalyst and aqueous tert-butyl hydroperoxide as an oxidant. This amidation reaction is operationally straightforward and provides primary, secondary, and tertiary amides in good to excellent yields for most cases utilizing inexpensive and readily available reagents under mild conditions. In situ formation of amine salts from free amines extends the substrate scope of the reaction. Chiral amides are also synthesized from their corresponding chiral amines without detectable racemization. The practicality of this amide formation reaction has been demonstrated in an efficient synthesis of the antiarrhythmic drug N-acetylprocainamide.
- Ghosh, Subhash Chandra,Ngiam, Joyce S. Y.,Seayad, Abdul M.,Tuan, Dang Thanh,Chai, Christina L. L.,Chen, Anqi
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p. 8007 - 8015,9
(2012/12/12)
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- Copper-catalyzed oxidative amidation of aldehydes with amine salts: Synthesis of primary, secondary, and tertiary amides
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A practical method for the amidation of aldehydes with economic ammonium chloride or amine hydrochloride salts has been developed for the synthesis of a wide variety of amides by using inexpensive copper sulfate or copper(I) oxide as a catalyst and aqueous tert-butyl hydroperoxide as an oxidant. This amidation reaction is operationally straightforward and provides primary, secondary, and tertiary amides in good to excellent yields for most cases utilizing inexpensive and readily available reagents under mild conditions. In situ formation of amine salts from free amines extends the substrate scope of the reaction. Chiral amides are also synthesized from their corresponding chiral amines without detectable racemization. The practicality of this amide formation reaction has been demonstrated in an efficient synthesis of the antiarrhythmic drug N-acetylprocainamide.
- Ghosh, Subhash Chandra,Ngiam, Joyce S.Y.,Seayad, Abdul M.,Tuan, Dang Thanh,Chai, Christina L.L.,Chen, Anqi
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p. 8007 - 8015
(2013/01/15)
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- Iron-catalyzed efficient synthesis of amides from aldehydes and amine hydrochloride salts
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A practical and efficient method for the synthesis of amides has been developed by iron-catalysed oxidative amidation of aldehydes with amine hydrochloride salts. A wide range of amides have been obtained in good to excellent yields under mild conditions. The application of this novel amide formation reaction to the synthesis of pharmaceutical compounds has been successfully demonstrated. Copyright
- Ghosh, Subhash Chandra,Ngiam, Joyce S. Y.,Chai, Christina L. L.,Seayad, Abdul M.,Dang, Tuan Thanh,Chen, Anqi
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supporting information; experimental part
p. 1407 - 1412
(2012/07/13)
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- Catalytic phosphorus(V)-mediated nucleophilic substitution reactions: Development of a catalytic appel reaction
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Catalytic phosphorus(V)-mediated chlorination and bromination reactions of alcohols have been developed. The new reactions constitute a catalytic version of the classical Appel halogenation reaction. In these new reactions oxalyl chloride is used as a consumable stoichiometric reagent to generate the halophosphonium salts responsible for halogenation from catalytic phosphine oxides. Thus, phosphine oxides have been transformed from stoichiometric waste products into catalysts and a new concept for catalytic phosphorus-based activation and nucleophilic substitution of alcohols has been validated. The present study has focused on a full exploration of the scope and limitations of phosphine oxide catalyzed chlorination reactions as well as the development of the analogous bromination reactions. Further mechanistic studies, including density functional theory calculations on proposed intermediates of the catalytic cycle, are consistent with a catalytic cycle involving halo- and alkoxyphosphonium salts as intermediates.
- Denton, Ross M.,An, Jie,Adeniran, Beatrice,Blake, Alexander J.,Lewis, William,Poulton, Andrew M.
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experimental part
p. 6749 - 6767
(2011/10/02)
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- Convenient one-pot synthesis of 2-oxazolines from carboxylic acids
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Simple one-pot methods for preparation of 2-oxazolines have been developed using 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMT-MM). Treatment of a mixture of carboxylic acids and 2-haloethylammonium salts with DMT-MM in methanol
- Hioki, Kazuhito,Takechi, Yumiko,Kimura, Noriyo,Tanaka, Hiroyuki,Kunishima, Munetaka
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experimental part
p. 1735 - 1737
(2009/10/10)
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- Highly efficient oxidative amidation of aldehydes with amine hydrochloride salts
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A mild and efficient copper-catalyzed oxidative amidation of aldehydes was developed using amine HCl salts and tert-butyl hydroperoxide as an oxidant. Copyright
- Yoo, Woo-Jin,Li, Chao-Jun
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p. 13064 - 13065
(2008/02/08)
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- Formation of N-Tributylstannyl Heterocycle from Bis(tributyltin) Oxide and ω-Haloalkyl Isocyanate. One-Pot Convenient Synthesis of 2-Oxazolidinones and Tetrahydro-2H-1,3-oxazin-2-one
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Novel types of compounds, N-tributylstannyl-2-oxazolidinone (4a) and tetrahydro-2H-1,3-oxazin-2-one (4b), are formed from the adduct of (n-Bu3Sn)2O (1) with ω-haloalkyl isocyanate (2), and the subsequent coupling reaction with alkyl halides gives a variety of N-substituted 2-oxazolidinones and tetrahydro-2-oxazinones in a one-pot procedure.Both the cyclization and the coupling reaction proceed quantitatively in the presence of HMPA which enhances the reactivity of the Sn-heteroatom bond by coordination.
- Shibata, Ikuya,Nakamura, Kenji,Baba, Akio,Matsuda, Haruo
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p. 853 - 859
(2007/10/02)
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- THE CONDENSATION REACTION BETWEEN ISOCYANATES AND CARBOXYLIC ACIDS. A PRACTICAL SYNTHESIS OF SUBSTITUTED AMIDES AND ANILIDES.
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Addition of a carboxylic acid to an isocyanate initially yields the mixed acid anhydride, decarboxylation of which leads to the N-substituted amide.The conversion of acid into amide was shown to proceed similarly for both aliphatic and aromatic carboxylic acids with a range of substituted isocyanates.
- Blagbrough, Ian S.,Mackenzie, Neil E.,Ortiz, Claudio,Scott, A. Ian
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p. 1251 - 1254
(2007/10/02)
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- Preparation of 2-haloethylamides
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2-Haloethylamides are prepared by reaction of 2-oxazolidinone or C1-6 alkyl or phenyl derivatives thereof with an acid halide.
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- The Use of 2-Oxazolidinone as a Latent Aziridine Equivalent. I. A Facile Method for the Preparation of 2-Substituted Oxazolines
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Ring-opening reaction of 2-oxazolidinone with acid chlorides followed by treatment with aqueous sodium hydroxide yields 2-substituted oxazolines.
- Poindexter, Graham S.
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p. 1431 - 1433
(2007/10/02)
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- Three Component Reactions. XIV. 2-Imidazolines and 1,2,4-Triazoles by Ring Closure Reactions of N-(2-Chloro-alkyl)imidchlorides with Hydrazine and Hydrazones
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N-(2-Chloro-alkyl)benzimidchlorides (1a and 1b) give with hydrazine in dependence on the reaction medium 1,1'-bis(2-imidazolines) (4), 1-benzamido-2-imidazolines (5) or 1,2,4-triazoles (6 and 7) and also N-(2-chloro-alkyl)benzamides (8).From imidchlorides
- Neumann, R.,Beger, J.
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p. 1026 - 1032
(2007/10/02)
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