Nucleophilic Addition of Amines to N-Aryl-substituted Pyrrolin-2-ones

The nucleophilic addition of n-butyl- and benzylamines to 1-(4-nitrophenyl)-5H-pyrrolin-5-one and 1-(4-sulfamoylphenyl)-5H-pyrrolin-2-one at 50°C in an excess of the amines with the formation of N-substituted amides of 3-alkyl(benzyl)amino-4-(4-R-anilino)butyric acids was investigated. The N-substituted amides of 3-arylamino-4-hydroxybutyric and 4-hydroxy-2-butenoic acids were synthesized from 2(5H)-furanone and aromatic amines (1:3) at 180°C. 4-Alkylamino-1-(4-nitrophenyl)pyrrolid-2-ones were obtained in the reaction of 1-(4-nitrophenyl)-5-pyrrolin-2-one with ammonia or aliphatic, alicyclic, and aromatic amines (1:3, 90°C, in DMF).     

Atom-economical brominations with tribromide complexes in the presence of oxidants

Bromination is an important transformation in organic synthesis, and novel efficient bromination techniques are still required. Herein, we demonstrate atom-economical brominations using (DMI)₂HBr₃, a novel tribromide complex, with oxidants such as DMSO and Oxone. Using this system, olefinic and aromatic brominations, as well as selective α-monobrominations of ketones proceeded well to afford the desired bromides in good yields. Importantly, in these reactions all of the bromine atoms in this complex are used to brominate.     

Nucleophilic Addition to Acetylenes in Superbasic Catalytic Systems: XIV. Vinilation of Diols in a System CsF-NaOH

A new catalytic system CsF-NaOH was developed for the synthesis of mono- and divinyl ethers of alkanediols exceeding in efficiency KOH. The nucleophilic addition of diols to acetylene in the presence of this system occurs both at enhance pressure (without solvent, 140–160°C) and atmospheric pressure (in DMSO medium, 100°C) of acetylene. Conditions were established of a selective preparation in a high yield of divinyl ethers from diols.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 5, 2005, pp. 677–683.Original Russian Text Copyright © 2005 by Oparina, Khil’ko, Chernyshova, Shaikhudinova, Parshina, Preiss, Henkelmann, Trofimov.     

烯丙基锡与芳香酰腙亲电加成反应的研究

报道了在Ｌｅｗｉｓ酸促进下三丁基烯丙基锡与芳香酰脘合成了Ｎ′－烯丙基芳香酰肼的一种新型的亲电加成反应。合成了７个未见文献报道的新化合物。其结构均经ＩＲ,＾１ＨＮＭＲ,＾１３ＣＮＭＲ,ＭＳ确证。该反应条件温和（室温即可进行）,选择性高,产率５０％－６０％。以酰腙和三丁基烯丙基锡摩尔比为１：２的反应也发现只有在Ｃ＝Ｎ上加成,而－Ｃ（＝Ｏ）－没有发生变化。     

Nucleophilic Addition of Oxindole to Pyrroloquinoxalinetriones

Russian Journal of Organic Chemistry - 3-Aroyl-5-phenylpyrrolo[1,2-a]quinoxaline-1,2,4(5H)-triones reacted with 2-oxindole to give products of addition of the C3H group of the enol form of...     

Heptalene Synthesis by Addition of Aryl Acetylenes to Azulenes

Russian Journal of Organic Chemistry - Aryl acetylenes bearing electron-withdrawing groups have been found that can add to azulenes and yield 1,2-substituted heptalenes. Theoretical studies of the...     

Addition of Secondary Amines to Alkynephosphonates

Addition of secondary amines to diethyl alkynephosphonates, catalyzed by Cu(I) salts, proceeds regio- and stereospecifically and yields diethyl (E)-2-diethylaminooalkenephosphonates. The E configuration was established by analysis of the vicinal coupling constants between the phosphorus and carbon nuclei in the ¹³C NMR spectra of the reaction products and model compounds: ³ JPC is 6-10 Hz at the cis arrangement of the coupled nuclei and 16 Hz or higher at the trans arrangement. In all the diethyl diethylaminoalkenephosphonates obtained, ³ JPC is about 5 Hz, suggesting cis addition.     

The Reaction of Electron-Deficient Cyclopropane Derivatives with Aromatic Amines

Abstract

N-Aryl-trans,trans-α-carboxyl-β-benzoyl-γ-aryl-γ-butyrolactams were synthesized in high yields with high stereoselectivity by the reaction of electron-deficient cyclopropane derivatives, cis-1-benzoyl-2-aryl-6,6-dimethyl-5,7-dioxo-spiro-[2 (a) Zhang , J. ; Blazecka , P. G. ; Davidson , J. G. First direct reductive amination of mucochloric acid: A simple and efficient method for preparing highly functionalized α,β-unsaturated γ-butyrolactams . Org. Lett. 2003 , 5 , 553 – 556 ; (b) Sarma, K. D.; Zhang, J.; Curran, T. T. Novel synthons from mucochloric acid: The first use of α,β-dichloro-γ-butenolides and γ-butyrolactams for direct vinylogous aldol addition. J. Org. Chem. 2007, 72, 3311–3318 . [Google Scholar] 5 (a) Chen , Y. L. ; Ding , W. Y. A simple approach to highly stereoselective synthesis of β γ-trans-γ-butyrolactones . Chem. J. Chin. Univ. 1998 , 19 , 1614 – 1616 ; (b) Chen, Y. L.; Ding, W. Y.; Cao, W. G.; Lu, C. Stereoselective synthesis of N-aryl-trans,trans-α-carboxyl-β-methoxycarbonyl-γ-aryl-γ-butyrolactones. Synth. Commun. 2002, 32, 1953–1960.  [Google Scholar]]-4,8-octadiones, with aromatic amines. The reaction mechanism was proposed.     

Nucleophilic Addition to Acetylenes in Superbasic Catalytic Systems: XIII. Fluoride Cesium Containing Systems,Efficient Catalysts for Alkanols Vinylation

New catalytic systems CsF-MOH (M = Li, Na) were developed for the synthesis of alkyl vinyl ethers comparable in efficiency to cesium alcoholates. The addition of primary and secondary alcohols to acetylene occurs in the presence of these systems at the atmospheric (DMSO, 100°C) or at enhanced (without solvent, 135–140°C) acetylene pressure and affords alkyl vinyl ethers in up to 93% yield.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 5, 2005, pp. 672–676.Original Russian Text Copyright © 2005 by Oparina, Shaikhudinova, Parshina1, Vysotskaya, Preiss, Henkelmann, Trofimov.     

Electron-Deficient Acetylenes as Three-Modal Adjuvants in SNH Reaction of Pyridinoids with Phosphorus Nucleophiles

Publications covering a new easy metal-free functionalization of pyridinoids (pyridines, quinolines, isoquinolines, acridine) under the action of the system of electron-deficient acetylenes (acetylenecarboxylic acid esters, acylacetylenes)/P-nucleophiles (phosphine chalcogenides, H-phosphonates) are reviewed. Special attention is focused on a S_N^H reaction of the regioselective cross-coupling of pyridines with secondary phosphine chalcogenides triggered by acylacetylenes to give 4-chalcogenophosphorylpyridines. In these processes, acetylenes act as three-modal adjuvants (i) activating the pyridine ring towards P-nucleophiles, (ii) deprotonating the P-H bond and (iii) facilitating the nucleophilic addition of the P-centered anion to a heterocyclic moiety followed by the release of the selectively reduced acetylenes (E-alkenes).     

Highly Efficient Michael Addition Reaction of Amines Catalyzed by Silica-Supported Aluminum Chloride

Aliphatic and aromatic amines undergo smooth nucleophilic addition to α,β-unsaturated compounds in the presence of a catalytic amount of silica-supported aluminum chloride at 60 °C and under solvent-free conditions to produce the corresponding β-amino compounds in excellent yields. This method is simple and convenient and works efficiently under mild conditions. This catalyst can used again without losing its activity three times.     

Microwave-Assisted Conjugate Addition of Pyrrole on Electron-Deficient Nitro-Olefins

Michael addition of pyrrole to β-nitrovinyl compounds were carried out using microwave methodology. Monosubstituted pyrroles were obtained selectively in a major amount. Formation of novel product obtained during one of the reactions was explained by the double addition to nitrostyrene.     

Nucleophilic Addition to Acetylenes in Superbasic Catalytic Systems: X. Catalytic Effect of Alkali Metal Hydroxides in the Vinylation of 1-Heptanol

The catalytic activity of alkali metal hydroxides in base-catalyzed addition of 1-heptanol to acetylene depends on the alkali metal nature and degree of hydration of its hydroxide. In a closed system, the catalytic activity of alkali metal hydroxides decreases in the series 2KOH·H₂O > RbOH·H₂O > CsOH·H₂O > NaOH. The corresponding series for a flow system is as follows: RbOH·H₂O > CsOH·H₂O > 2KOH·H₂O > NaON > KOH·H₂O. The difference is explained by participation of the catalyst in side reactions with both 1-heptanol and acetylene. Addition of dimethyl sulfoxide to the catalytic system accelerates the vinylation process.     

Facile Addition of Dichloroketene to Acetylenes Mediated by Zinc and Ultrasound

The addition of dichloroketene, generated from trichloroacetyl chloride, zinc dust and ultrasound, to terminal and internal acetylenes is reported. This procedure is a more convenient alternative to Zn-Cu couple.     

SNHAr Reaction of Pyridines with Bis(polyfluoroalkyl)phosphonates Assisted by Electron-Deficient Acetylenes

Russian Journal of General Chemistry - The SNHAr reaction of pyridines with bis(polyfluoroalkyl)phosphonates assisted by benzoylphenylacetylene (equimolar reactants ratio, 70–75°С,...     

Direct Nucleophilic Addition to N‐Alkoxyamides

While the synthesis of amide bonds is now one of the most reliable organic reactions, functionalization of amide carbonyl groups has been a long‐standing issue due to their high stability. As an ongoing program aimed at practical transformation of amides, we developed a direct nucleophilic addition to N‐alkoxyamides to access multisubstituted amines. The reaction enabled installation of two different functional groups to amide carbonyl groups in one pot. The N‐alkoxy group played important roles in this reaction. First, it removed the requirement for an extra preactivation step prior to nucleophilic addition to activate inert amide carbonyl groups. Second, the N‐alkoxy group formed a five‐membered chelated complex after the first nucleophilic addition, resulting in suppression of an extra addition of the first nucleophile. While diisobutylaluminum hydride (DIBAL‐H) and organolithium reagents were suitable as the first nucleophile, allylation, cyanation, and vinylation were possible in the second addition including inter‐ and intramolecular reactions. The yields were generally high, even in the synthesis of sterically hindered α‐trisubstituted amines. The reaction exhibited wide substrate scope, including acyclic amides, five‐ and six‐membered lactams, and macrolactams.