Reactions of relevance to the chemistry of aminoglycoside antibiotics. Part 9. New reagents for amination of the ethylenic linkage

Barton, Derek H. R.; Britten-Kelly, Michael R.; Ferreira, Daneel

doi:10.1039/p19780001682

Cited by 25 publications

(5 citation statements)

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“…Preparation of N,N -Diisopropyl-2-[(2,5-dimethyl-4- tert -butyl-phenyl)thio]ferrocenecaboxamide (34). To a stirred solution of arenelithium ( 39 ) was added bis(2,5-dimethyl-4- tert -butylphenyl) disulfide (3.86 g, 10 mmol in 8 mL of dry THF) via syringe over 30 min at −78 °C. The reaction mixture was worked up and purified by column chromatography using petroleum ether (60−80 °C) and ethyl acetate (19:2) to afford the desired compound as an orange solid.…”

Section: Methodsmentioning

confidence: 99%

Protection against Peroxynitrite-Mediated Nitration Reaction by Intramolecularly Coordinated Diorganoselenides

2005

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A series of intramolecularly Se···X (X = N, O) coordinated diorganoselenides and -sulfides are synthesized by using the heteroatom-directed lithiation route and characterized by multinuclear (1H, 13C, 77Se) NMR, IR spectroscopy, and electrospray mass spectrometry (ES-MS). The intramolecular Se···O interactions in diorganoselenides 26−31 have been studied by multinuclear NMR studies in solution and in the solid state by single-crystal X-ray crystallography. The protection against peroxynitrite-mediated nitration reaction (PN assay) by diorganoselenides/-sulfides (with and without intramolecular coordination) has been evaluated. The PN assay data of diorganoselenides reveal that the selenides 20−22, having a basic amino group (sp3-N donor) in close proximity of selenium, are more active compared to the diorganoselenides 16−19, having an imino group (sp2-N donor), and also show much higher protective action than the unsubstituted diorganoselenides 14 and 15. The diorganoselenides 16−31 were oxidized to corresponding selenoxides 44−59. The redox properties of the selenoxides 13 and 44−59 have been investigated by cyclic voltammetry and potentiometric titration experiments. Two redox potentials for in situ-generated ferrocenyl selenoxides (50, 54−59) were observed. The reduction of selenoxides 13 and 48 to ebselen (2) and selenide 20 with benzenethiol (PhSH) was monitored by ES-MS.

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Section: Methodsmentioning

confidence: 99%

Protection against Peroxynitrite-Mediated Nitration Reaction by Intramolecularly Coordinated Diorganoselenides

2005

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“…24 β-Hydroxyamines, aziridines, and vicinal diamines can be obtained in one-pot procedures. Aminations or related reactions such as diamination or oxyaminations can also be promoted by the use of stoichiometric amounts of Hg(II) salts, 24,64,220 Tl(III) salts, 24 Cu(OAc) 2 , 65 Co complexes, 66 or seleno and sulfo derivatives, 67,68 as well as Fe(II) complexes. 12 In all these cases the aforementioned rules regarding selectivity and reactivity are applicable vide infra.…”

Section: Activation Of the Olefin A Stoichiometric Use Of Transition ...mentioning

confidence: 99%

Metal-Initiated Amination of Alkenes and Alkynes

1998

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ContentsI. Introduction 675 II. Mechanism and Coordination Chemistry 676 1. Activation of the Olefin 677 a. Stoichiometric Use of Transition Metals 677 b. Making the Reaction Catalytic 679 2. N−H Activation by Alkali Metals 680 3. Activation of the N−H Bond by Early Transition Metals, Lanthanides, and Actinides 681 4. Activation of the N−H Bond by Late Transition Metals 684 III. Synthetic Applications of Catalytic Aminations 686 1. Aminations Catalyzed by Zeolites 686 2. Aminations Assisted by Alkali Metals 686 a. Ethylene 686 b. Aliphatic Olefins 687 c. Styrenes 688 d. 1,3-Butadienes 689 3. Aminations Catalyzed by Transition Metals 690 a. Palladium-Catalyzed Aminations of Olefins 690 b. Other Catalytic Oxidative Aminations of Olefins 693 c. Amination of Allenes 693 d. Intramolecular Amination of Alkynes 694 e. Intramolecular Amination of Alkenes 695 f. Tandem Cyclization Reactions of Aminoalkynes and -alkenes 697 g. Intermolecular Hydroamination Reactions 698 IV. Summary and Conclusions 699 V. Acknowledgments 700 VI. References 700

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“…Chloramine-T (CT) is a well-known commercially available oxidizing agent, which can be used as a source of chloronium cations, nitrogen anions, or both . As a result, CT has enjoyed widespread use in syntheses because of its reactivity toward a wide variety of functional groups . The most impressive synthetic methodology to date, in which CT is used as a nitrogen source, was reported by Sharpless and co-workers.…”

Section: Synthesis Of Aziridines From Olefins Using Haloamine-tmentioning

confidence: 99%

Utilization of N−X Bonds in The Synthesis of N-Heterocycles

Minakata

2009

Acc. Chem. Res.

142

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Nitrogen-containing heterocycles--such as aziridines, pyrrolidines, piperidines, and oxazolines--frequently show up as substructures in natural products. In addition, some of these species show potent biological activities. Therefore, researchers would like to develop practical and convenient methods for constructing these heterocycles. Among the available methods, the transfer of N(1) units to organic molecules, especially olefins, is a versatile method for the synthesis of N-heterocycles. This Account reviews some of our recent work on the synthesis of N-heterocycles using the N-X bond. A nitrogen-halogen bond bearing an electron-withdrawing group on the nitrogen can be converted to a halonium ion. In the presence of C-C double bonds, these species produce three-membered cyclic halonium intermediates, which can be strong electrophiles and can produce stereocontrolled products. N-Halosuccinimides are representative sources of halonium ions, and the nitrogen of succinimide is rarely used in organic synthesis. If the nitrogen could act as a nucleophile, after releasing halonium ions to C-C double bonds, we expect great advances would be possible in the stereoselective functionalization of olefins. We chose N-chloro-N-sodio-p-toluenesulfonamide (chloramine-T, CT), an inexpensive and commercially available reagent, as our desired reactant. In the presence of a catalytic amount of CuCl or I(2) and AgNO(3), we achieved the direct aziridination of olefins with CT. The reaction catalyzed by I(2) could be carried out in water or silica-water as a green process. The reaction of iodoolefins with CT gave pyrrolidine derivatives under extremely mild conditions with complete stereoselectivity. We also extended the utility of the N-chloro-N-metallo reagent, which is often unstable and difficult to work with. Although CT does not react with electron-deficient olefins without a metal catalyst or an additive, we found that N-chloro-N-sodiocarbamates react with electron-deficient olefins in the presence of a phase transfer catalyst to give the corresponding aziridines. We also used this method to synthesize asymmetric aziridines using quaternary cinchona alkaloid catalysts. We also developed a facile synthetic method for preparing N-heterocycles that involves the in situ generation of an N-X bond using tert-butyl hypochlorite or tert-butyl hypoiodite (tert-BuOI). Treatment of alkenylamides containing an active hydrogen on the nitrogen with tert-BuOI led to the production of various N-heterocycles via intramolecular cyclization. Iodination of readily available sulfonamides or carboxamides with tert-BuOI generated reactive N-iodinated amides, which smoothly reacted with olefins to give aziridines or oxazolines. The reaction of fullerene, C(60), with CT also led to aziridination: the resulting aziridinofullerene underwent a unique rearrangement to an azafulleroid. Chlorination of readily available amide derivatives with tert-BuOCl, followed by a reaction with C(60) in the presence of an organic base, afforded aziridinofullerenes with...

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Reactions of relevance to the chemistry of aminoglycoside antibiotics. Part 9. New reagents for amination of the ethylenic linkage

Cited by 25 publications

References 0 publications

Protection against Peroxynitrite-Mediated Nitration Reaction by Intramolecularly Coordinated Diorganoselenides

Protection against Peroxynitrite-Mediated Nitration Reaction by Intramolecularly Coordinated Diorganoselenides

Metal-Initiated Amination of Alkenes and Alkynes

Utilization of N−X Bonds in The Synthesis of N-Heterocycles

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