- Alicyclophanes: A new range of cyclophanes containing rigid alicyclic subunits in place of the aromatic rings
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Norbornenosuccinimides have been coupled stereoselectively with 2,5- bis(trifluoromethyl-1,3,4-oxadiazole to prepare alicyclic scaffolds 5 and 20. Alkylations of the terminal succinimido-nitrogens of 5 with bis-alkylating agents have produced macrocyclic compounds in a short, high-yielding procedure. Alicyclophanes containing one scaffold subunit were obtained from 1,6-dibromohexane, 1,5-dichloro-3-oxapentane, 1,11-dibromo-3,6,9- trioxaundecane and 9,10-bis(chloromethyl)anthracene. Larger alicyclophanes incorporating two spacer subunits were formed by intermolecular cyclisation of 5 with 1,2-dibromoethane or 19 with m- or p-xylylene dibromide. Reaction of 5 with propargyl bromide, followed by oxidative coupling (CuCl) of the pendant acetylenes provided bis-acetylenic alicyclophane 13. (C) 2000 Elsevier Science Ltd.
- Butler, Douglas N.,Shang, Muhong,Warrener, Ronald N.
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Read Online
- Pyrrolidine synthesis on polystyrene supports: Development of a 'one-pot' dipolar cycloaddition strategy
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Preparation of substituted pyrrolidines was achieved by solid-phase synthesis via a room temperature 1,3-dipolar cycloaddition of a silver-azomethine ylide, generated in situ, with a polymer-supported maleimide.
- Barrett, Anthony G.M.,Boffey, Raymond J.,Frederiksen, Mathias U.,Newton, Christopher G.,Roberts, Richard S.
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Read Online
- Inverse electron-demand Diels-Alder (iEDDA) bioorthogonal conjugation of half-sandwich transition metallocarbonyl entities to a model protein
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Novel transition metallocarbonyl complexes carrying a norbornene or an oxanorbornene group were synthesized by [4 + 2] cycloaddition between the organometallic maleimide dienophiles and cyclopentadiene or furan, respectively. The oxanorbornene adduct was obtained as a mixture of endo and exo isomers as confirmed by X-ray diffraction and NMR spectroscopy. The (oxa)norbornene groups further provided convenient chemical reporters to carry out inverse electron demand Diels-Alder (iEDDA) reactions with tetrazine derivatives. Detailed kinetic studies with a model tetrazine revealed that faster rates of reaction were determined with both isomers of the oxanorbornene complex with respect to the norbornene complexes. Eventually, incorporation of metallocarbonyl entities into bovine serum albumin equipped with tetrazine handles was achieved as shown by IR spectroscopy of the protein conjugates.
- Fischer-Durand, Nathalie,Jamroz, Daria,Jarzyński, Szymon,Palusiak, Marcin,Rudolf, Bogna,Salmain, Michèle,St?pniewska, Marlena,Wojtulewski, S?awomir
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- PROCESS FOR THE INDUSTRIAL SYNTHESIS OF LURASIDONE
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Disclosed is a process for the industrial synthesis of Lurasidone from (1R,2R)-cyclohexane-1,2-diyldimethanol (1), 3-(piperazin-1- yl)benzo[d]isothiazole (3) and (3aR,4R,7R,7aS)-3a,4,7,7a-tetrahydro-4,7- methanoisobenzofuran-1,3-dione (6).). Said process is optimised to obtain Lurasidone with high yields and high purities by preparing highly pure synthesis intermediates, using critical raw materials and reagents in amounts close to the stoichiometric amounts, increasing productivity and reducing the costs and environmental impact of the process.
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(2015/05/05)
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- Quinoline-functionalized norbornene for fluorescence recognition of metal ions
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A quinoline-functionalized norbornene (1) and its homopolymer (P1) for metal ions recognition have been synthesized and characterized. In CH3CN solution, 1 exhibited fluorescence enhancement response toward Hg2+, Zn2+ and Cu2+, with Hg2+ resulting in a green emission at 465 nm, and Zn2+/Cu2+ increasing 1's original emission at 406 nm. NMR titrations and DFT calculations results indicated that 1 bound Hg2+ in an imidic acid tautomeric form of the amide quinoline receptor, while Zn2+ and Cu2+ were bound to 1 in an amide tautomeric form. In addition, owing to the strong imidic acid tautomeric binding mode of 1-Hg2+ complex, 1 can recognized Hg2+ from Zn2+/Cu2+ and other competitive metal ions. In contrast, the homopolymer P1, which was obtained by ring opening metathesis polymerization (ROMP) method, exhibited only fluorescence enhancement sensing to Hg2+ and Cu2+ in an amide tautomeric binding mode with increasing emission at 416 nm.
- Yao, Pei-Shui,Cao, Qian-Yong,Peng, Rong-Peng,Liu, Jing-Hua
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- IBX-mediated oxidation of unactivated cyclic amines: application in highly diastereoselective oxidative Ugi-type and aza-Friedel-Crafts reactions
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The first o-iodoxybenzoic acid (IBX) mediated oxidation of unactivated amines to imines is described. A range of meso-pyrrolidines were shown to be suitable substrates. The chemical space was further explored with one-pot oxidative Ugi-type and aza-Friedel-Crafts reactions, which proved to be highly diastereoselective.
- De Graaff,Bensch,Van Lint, Matthijs J.,Ruijter,Orru
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supporting information
p. 10108 - 10112
(2015/10/20)
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- Synthesis of [1]benzothieno[3,2-b][1]benzothiophene pendant and norbornene random co-polymers via ring opening metathesis
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2-Octyl-7-(11-(cis-5-norbornene-endo-2,3-dicarboxylicimide)undecane)[1] benzothienopheno[3,2-b] benzothienophene (1) was synthesised and co-polymerised with varying amounts of 1-decyl(cis-5-norbornene-endo-2,3-dicarboxylic) imide (2) or norbornene, using a ruthenium catalyst, to produce a series of random co-polymers.
- Combe, Craig M. S.,Biniek, Laure,Schroeder, Bob C.,McCulloch, Iain
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p. 538 - 541
(2014/01/06)
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- AMIDOALKYLPIPERAZINYL DERIVATIVES FOR THE TREATMENT OF CENTRAL NERVOUS SYSTEM DISEASES
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The invention relates to novel amidoalkylpiperazinyl derivatives of tricyclic heterocyclic systems of general formula (I), wherein Z represents -NH- and X represents -S-, or Z represents -S- and X represents >C=C1 represents H or -CH3, R6 and R7 both represent H, n is an integer from 0 to 4 inclusive, G represents a cyclic amide or imide moiety, and optical isomers, geometric isomers, and pharmaceutically acceptable salts thereof. The compounds may be useful for the treatment and/or prevention of the central nervous system disorders.
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Page/Page column 28; 29
(2013/03/26)
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- Mechanochemical Diels-Alder cycloaddition reactions for straightforward synthesis of endo-norbornene derivatives
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Under mechanochemical milling conditions, Diels-Alder cycloaddition of cyclopentadiene with maleic anhydride and maleimide derivatives proceeded very smoothly, affording endo-norbornenes exclusively in quantitative yield. All the transformations were accomplished at room temperature without using any catalyst or organic solvent, thus the workup and purification procedure is very simple. Control experiments on traditional and other tentative conditions were also investigated. Georg Thieme Verlag Stuttgart - New York.
- Zhang, Ze,Peng, Zhi-Wei,Hao, Ming-Feng,Gao, Jian-Gang
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scheme or table
p. 2895 - 2898
(2011/02/23)
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- Enantioselective synthesis of tricyclic amino acid derivatives based on a rigid 4-azatricyclo[5.2.1.02,6]decane skeleton
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An enantioselective route to four tricyclic amino acids and N-tosylamides, composed of a central norbornane framework with a 2-endo,3-endo-annelated pyrrolidine ring and a 5-endo-C1 or -C2 side chain, has been developed. A key intermediate was the chiral, N-Boc-protected ketone (1R,2S,6S,7R)-4-azatricyclo[5.2.1.02,6]decan-8-one, available from inexpensive endo-carbic anhydride in five steps and 47% yield. The rigid scaffold makes these amino acid derivatives promising candidates for β-turn-inducing building blocks in peptidomimetics and for chiral auxiliaries in asymmetric organocatalysis.
- Breuning, Matthias,Haeuser, Tobias,Mehler, Christian,Daeschlein, Christian,Strohmann, Carsten,Oechsner, Andreas,Braunschweig, Holger
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supporting information; experimental part
(2010/04/22)
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- Photo-induced molecular-recognition-mediated adhesion of giant vesicles
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Few methods currently exist for controlling vesicle-vesicle adhesion. We now report a new system, based upon a multivalent guest and an amphiphilic receptor with a photo-isomerisable anchor that can be incorporated into lipid vesicles of different sizes.
- Mansfeld, Friederike M.,Feng, Guoqiang,Otto, Sijbren
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experimental part
p. 4289 - 4295
(2009/12/06)
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- N-[4-(arylpiperazin-1-yl)butyl]bicyclo[2.2.1]hept-5-ene-endo-2, endo-3-dicarboximides and Their Epoxy Derivatives. Synthesis and affinity for 5-HT1a receptors
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New ligands for 5-HT1A serotonin receptors, N-[4-(4- arylpiperazin-1-yl)butyl]bicyclo[2.2.1]hept-5-ene-endo-2,endo-3-dicarboximides and their epoxy derivatives, were synthesized, and their affinity for 5-HT 1A receptors was estimated at 16.2 ± 2.0 to 0.60 ± 0.08 nM.
- Makan,Tsymbal,Soboleva,Tarabara,Kas'Yan,Andronati
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body text
p. 292 - 296
(2009/08/14)
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- Ring-opening Cross-metathesis (ROCM) as a novel tool for the ligation of peptides
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The development of ring-opening cross-metathesis (ROCM) as a novel tool for the site-specific ligation of peptide units is reported. The resulting structural units at the site of ligation resulting from ROCM resemble proline as well as other known ss-turn
- Michaelis, Simon,Blechert, Siegfried
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p. 2358 - 2368
(2008/02/04)
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- Synthesis, structure, and transformations of new endic anhydride derivatives
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4-Azatricyclo[5.2.1.02,6]dec-8-ene and its N-phenyl derivative were synthesized by reaction of endic anhydride with amines, transformation of the amido acids thus obtained to imides, and subsequent reduction of the latter with lithium aluminum hydride. The unsubstituted tricyclic amine was brought into reactions with electrophilic reagents: p-toluenesulfonyl chloride, p-toluoyl chloride, m-tolyl isocyanate, phenyl isothiocyanate, and endic anhydride to obtain a number of new derivatives; also, the corresponding salt with 1-adamantanecarboxylic acid was isolated. N-(p-Tolylsulfonyl)- and N-(m-tolylcarbamoyl)-4-azatricyclo[5.2.1.02,6]dec-8-enes were oxidized to the corresponding 8,9-epoxy derivatives with monoperoxyphthalic acid. The structure of the products was confirmed by the data of IR, 1H and 13C NMR, and mass spectra. The molecular structures of N-(p-iodophenyl)bicyclo[2.2.1]hept-2-ene-endo-5,endo-6-dicarboximide and N-phenyl-4-azatricyclo[5.2.1.02,6]dec-8-ene were established by X-ray analysis.
- Tarabara,Kas'yan,Krishchik,Shishkina,Shishkin,Kas'yan
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p. 1299 - 1308
(2007/10/03)
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- Nonreductive enantioselective ring opening of N-(methylsulfonyl)dicarboximides with diisopropoxytitanium α,α,α′,α′-tetraaryl-1,3-dioxolane-4,5- dimethanolate
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The bicyclic and tricyclic meso-N-(methylsulfonyl)dicarboximides 1a-f are converted enantioselectively to isopropyl [(sulfonamido)carbonyl]-carboxylates 2a-f by diisopropoxytitanium TADDOLate (75-92% yield; see Scheme 3). The enantiomer ratios of the products are between 86:14 and 97:3, and recrystallization from CH2Cl2/hexane leads to enantiomerically pure sulfonamido esters 2 (Scheme 3). The enantioselectivity shows a linear relationship with the enantiomer excess of the TADDOL employed (Fig. 3). Reduction of the ester and carboxamide groups (LiAlH4) and additional reductive cleavage of the sulfonamido group (Red-Al) in the products 2 of imide-ring opening gives hydroxy-sulfonamides 3 and amino alcohols 4, respectively (Scheme 4). The absolute configuration of the sulfonamido esters 2 is determined by chemical correlation (with 2a, b; Scheme 6), by the X-ray analysis of the camphanate of 3e (Fig. I), and by comparative 19F-NMR analysis of the Mosher esters of the hydroxy-sulfonamides 3 (Table I). A general proposal for the assignment of the absolute configuration of primary alcohols and amines of Formula HXCH2CHR1R2, X = O, NH, is suggested (see 11 in Table I). It follows from the assignment of configuration of 2 that the Re carbonyl group of the original imide 1 is converted to an isopropyl ester group. This result is compatible with a rule previously put forward for the stereochemical course of reactions involving titanium TADDOLate activated chelating electrophiles (12 in Scheme 7). A tentative mechanistic model is proposed (13 and 14 in Scheme 7).
- Ramon, Diego J.,Guillena, Gabriela,Seebach, Dieter
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p. 875 - 894
(2007/10/03)
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- Metal Carbonyl Complexes with Anions of Cyclic Imides
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A large series of metal carbonyl complexes with N-bonded anions of various cyclic imidates (X(-)) has been prepared: (-), (-), (-) (M = Cr, Mo, W), Re(CO)5X, (-), (-).Also pyromellitdiimidate and cyclopentanebis(dicarboximidate) bridged complexes (2-) (M = Cr, Mo, W) and the dicyanamide complex (-) have been obtained.Reactions at the coordinated imidate ligands and the spectroscopic data of the complexes are reported. - Keywords: Chromium, Molybdenum, Tungsten, Manganese Carbonyls, Anions of Cyclic Imides as Ligands
- Schier, Ernst-Juergen,Sacher, Wolfgang,Beck, Wolfgang
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p. 1424 - 1434
(2007/10/02)
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- PHASE TRANSITIONS IN BICYCLIC COMPOUNDS.
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The thermal properties of bicyclic and cyclic compounds obtained by DSC show that substituents such as the anhydride, nitrile, and carbonyl groups retain the polymorphic phase properties of the parent ring systems while groups such as the imide, methylimide, and carboxylic acid exclude the appearance of a disordered solid phase. The phase properties of chloro and hydroxyl derivatives investigated and more varied and depend on the position of these groups on the ring. The variety of compounds studied shows that hysteresis is a common occurrence in all of these ring systems.
- Weinstein,Leffler,Currie
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- Nitrosamine Photolysis as a Synthetic Method: The Addition of Aminium Radicals to Unsaturated Carbon-Carbon Bonds
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Acid complexed nitrosamines decompose from their lowest singlet excited state to gine aminium radicals and nitric oxide radical transients.Aminium radicals initiate addition of various unsaturated groups to give 1-amino-2-nitroso compounds under an inert atmosphere, or 1-amino-2-nitrates under oxygen.In this report, photoaddition of nitroamines to olefins, acetylenes and fused aromatic hydrocarbons, and the subsequent transformations of the intermediates are described.Aminium radical initiated intramolecular cyclization to prepare tetracyclic aza compounds is also described.While photoaddition of nitrosamines to 4-propenylanisole or 3-butenol wes efficient, that to 3-butenyl benzoates under oxidative conditions was only fair, obviously due to the presence of a benzene ring.The oxidative photoaddition to 3-butenyl halide was followed by spontaneous cyclization to an azaspiro compound.The photoaddition to phenyl-substituted acetylenes gave β-nitroso enamines which hydrolyzed to diketomonoximes under neitral conditions but decomposed extensively under acidic conditions.Certain fused aromatic hydrocarbons acted as singlet sensitizers as well as substrates to induce similar addition giving amino nitroso adducts.These adducts took different courses of conversion dependent on reaction conditions, and on steric and electronic factors.
- Chow, Yuan L.,Colon, Carlos J.,Chang, Dawid W. L.,Pillay, K. Somasekharen,Lochart Robert D.,Tezuka, Takahiro
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p. 622 - 634
(2007/10/02)
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- SYNTHESIS OF COMPOUNDS OF THE BICYCLOHEPTANE SERIES THAT ARE FUSED WITH AN OXAZECINE RING
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Derivatives of the bicycloheptane series that are condensed with an oxazecine ring were obtained.A number of transformations of the compounds obtained were realized.Data from the IR, NMR, and mass spectra that confirm the structures of the synthesized compounds are presented.
- Levchenko, N. K.,Segal', G. M.,Torgov, I. V.
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p. 251 - 256
(2007/10/02)
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