- Metal-Free Domino Oligocyclization Reactions of Enynals and Enynones with Molecular Oxygen
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A novel metal-free direct addition of molecular oxygen to the C-C triple bond toward benzannulated oxygen-bridged seven-membered ring systems and aza[3.1.0]bicycle skeletons under 3O2 atmosphere has been described. The reaction proceeds through at least three intramolecular C-O and C-C bond forming steps via green, simple, and unprecedented domino radical processes with high selectivity and good yields.
- Abbasi Kejani, Alireza,Khosravi, Hormoz,Rominger, Frank,Balalaie, Saeed,Breit, Bernhard
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supporting information
p. 1291 - 1295
(2021/02/20)
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- Efficient Synthesis of N-Benzyloxycarbonyl-2-aminoalkanesulfonyl Chlorides with Functionalized Side Chains
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N-Benzyloxycarbonyl (Cbz)-protected 2-aminoalkanesulfonyl chlorides are useful building blocks for the synthesis of sulfonopeptides, which are receptor ligands and enzyme inhibitors, and are prepared by the coupling reaction of N-protected aminoalkanesulfonyl chlorides with amino acid or peptide esters. Various N-Cbz-protected 2-aminoalkanesulfonyl chlorides with functionalized side chains were synthesized through the radical addition of different xanthates to benzyl N-allylcarbamate and subsequent oxidative chlorination with tert-butyl hypochlorite under neutral conditions. A mechanism for the oxidative chlorination is proposed. This is a useful and convenient strategy for the synthesis of N-Cbz-protected 2-aminoalkanesulfonyl chlorides with diverse functionalized side-chains.
- Abdellaoui, Hassane,Chen, Xingpeng,Xu, Jiaxi
-
p. 2250 - 2256
(2017/05/05)
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- M1 RECEPTOR POSITIVE ALLOSTERIC MODULATOR COMPOUNDS AND METHODS OF USE THEREOF
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The present invention is directed to compounds of Formula (I): and pharmaceutically acceptable salts thereof, wherein Q, X, Y, Z, R1, R7 and n are defined herein. The compounds of Formula (I) are M1 receptor positive allosteric modul
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Page/Page column 46
(2017/09/15)
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- CONTRAST AGENTS
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The present invention relates to new class of functionalized polyazamacrocycles including at least one phosphonic or phosphinic group linked to a nitrogen atom of the macrocyclic cage, and capable of chelating paramagnetic metal ions, their chelated compl
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Page/Page column 30
(2017/11/10)
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- SILICON BASED DRUG CONJUGATES AND METHODS OF USING SAME
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Described herein are silicon based conjugates capable of delivering one or more payload moieties to a target cell or tissue. Contemplated conjugates may include a silicon-heteroatom core, one or more optional catalytic moieties, a targeting moiety that permits accumulation of the conjugate within a target cell or tissue, one or more payload moieties (e.g., a therapeutic agent or imaging agent), and two or more non-interfering moieties covalently bound to the silicon-heteroatom core.
- -
-
Paragraph 0478; 0481; 0482
(2017/08/07)
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- Convenient syntheses of phosphinic analogues of γ-aminobutyric- and glutamic acids
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Three-steps, one-pot synthesis of 2-amino-4-(hydroxyphosphinyl)butyric acid from dibutyl ester of vinylphosphinic acid was carried out with an overall yield of 66%. 3-Aminopropylphosphinic acid was prepared from allylamine in three steps with an overall y
- Khomutov,Formanovsky,Mikhura,Vepsalainen,Kochetkov,De Biase,Khomutov
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p. 672 - 676
(2017/01/28)
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- Enantioselective and Regiodivergent Functionalization of N-Allylcarbamates by Mechanistically Divergent Multicatalysis
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A pair of mechanistically divergent multicatalytic reaction sequences has been developed consisting of nickel-catalyzed isomerization of N-allylcarbamates and subsequent phosphoric-acid-catalyzed enantioselective functionalization of the resulting intermediates. By appropriate selection of reaction partners, in situ generated imines and ene-carbamates are mechanistically partitioned to yield opposing functionalized products. Formal α-functionalization to give protected α-arylamines is achieved upon enantioselective Friedel–Crafts reaction with arene nucleophiles, whereas formal β-functionalization is achieved upon reaction with diarylimine electrophiles in an enantioselective Povarov-[4+2] cycloaddition.
- Richmond, Edward,Khan, Ismat Ullah,Moran, Joseph
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supporting information
p. 12274 - 12277
(2016/08/24)
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- Hexahydro-1 H -Isoindolinone-Like Scaffolds from Electronically Deactivated and Sterically Hindered Dienes: Synthesis in the Context of Muironolide A
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Initial synthetic efforts toward muironolide A based upon an intramolecular Diels-Alder strategy were hampered by a conjugate reduction rather than the desired half-reduction. An intermolecular Diels-Alder strategy was initiated that utilized electronically deactivated and sterically hindered dienes. The [4+2] cycloadditions were successful, but only with highly reactive dipolarophiles such as N-phenylmaleimide and 4-phenyl-1,2,4-triazoline-3,5-dione thus establishing the scope of these dienes. Although limited, installation of the α,β-unsaturated lactam embedded in the hexahydro-1H-isoindolinone is noteworthy.
- Olson, Christopher A.,Shaner, Courtnay E.,Roche, Sydney C.,Ferrence, Gregory M.,Mitchell, T. Andrew
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p. 2756 - 2766
(2015/09/15)
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- SELECTIVE OCTAHYDRO-CYCLOPENTA[C] PYRROLE NEGATIVE MODULATORS OF NR2B
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Compounds that selectively negatively modulate NMDA receptors containing an NR1/NR2B subunit, pharmaceutical compositions comprising the compounds, and methods of treating a disease using the compounds are disclosed. Such diseases include, without limitation, neurological dysfunction such as Parkinson's disease, Huntington's disease, amyotrophic lateral sclerosis, multiple sclerosis, and seizure disorders; emotional disorders; depression; bipolar disorder; obsessive-compulsive disorder; and other anxiety disorders.
- -
-
Paragraph 0116
(2015/04/15)
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- N-Urethane protection of amines and amino acids in an ionic liquid
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An efficient, solvent-free protocol for the N-fluorenylmethoxycarbonylation and N-benzyloxycarbonylation of amines is described. The reaction of aliphatic and aromatic amines with FmocOSu and Cbz-Osu in [Bmim][BF4] at room temperature afforded the corresponding N-urethane derivatives in excellent yields and do not require any further purification. The method has been extended to the N-Fmoc and N-Cbz protection of amino acids. Absence of bases, very short reaction times, high yields, selectivity and ease of product separation are some advantages of this protocol.
- Di Gioia,Gagliardi,Leggio,Leotta,Romio,Liguori
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p. 63407 - 63420
(2015/08/11)
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- Expeditious synthesis of 1-substituted taurines with diverse functionalized side-chains
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A radical addition reaction and subsequent performic acid oxidation were used for the synthesis of 1-substituted taurines with diverse functionalized side-chains from N-allylphthalimide and various xanthates. The current approach shows high yields and short synthetic route and reaction time. Moreover, the current method is a convenient and practical method for the synthesis of 1-substituted taurines with different functionalized side-chains.
- Kakaei, Saeed,Chen, Ning,Xu, Jiaxi
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p. 302 - 309
(2013/01/15)
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- One-point binding ligands for asymmetric gold catalysis: Phosphoramidites with a TADDOL-related but acyclic backbone
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Readily available phosphoramidites incorporating TADDOL-related diols with an acyclic backbone turned out to be excellent ligands for asymmetric gold catalysis, allowing a number of mechanistically different transformations to be performed with good to outstanding enantioselectivities. This includes [2 + 2] and [4 + 2] cycloadditions of ene-allenes, cycloisomerizations of enynes, hydroarylation reactions with formation of indolines, as well as intramolecular hydroaminations and hydroalkoxylations of allenes. Their preparative relevance is underscored by an application to an efficient synthesis of the antidepressive drug candidate (-)-GSK 1360707. The distinctive design element of the new ligands is their acyclic dimethyl ether backbone in lieu of the (isopropylidene) acetal moiety characteristic for traditional TADDOLs. Crystallographic data in combination with computational studies allow the efficiency of the gold complexes endowed with such one-point binding ligands to be rationalized.
- Teller, Henrik,Corbet, Matthieu,Mantilli, Luca,Gopakumar, Gopinadhanpillai,Goddard, Richard,Thiel, Walter,Fuerstner, Alois
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supporting information
p. 15331 - 15342
(2012/11/07)
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- COMPOUNDS FOR TREATING DISORDERS MEDIATED BY METABOTROPIC GLUTAMATE RECEPTOR 5, AND METHODS OF USE THEREOF
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Provided herein are compounds and methods of synthesis thereof. The compounds provided herein are useful for the treatment, prevention, and/or management of various disorders, such as neurological disorders, psychiatric disorders, neuromuscular disorders, gastrointestinal disorders, lower urinary tract disorder, and cancer. Compounds provided herein modulate the activity of metabotropic glutamate receptor 5 (mGluR5) in the central nervous system or the periphery. Pharmaceutical formulations containing the compounds and their methods of use are also provided herein.
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Page/Page column 161-162
(2010/11/03)
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- Gold(l)-Catalyzed amination of allylic alcohols with cyclic ureas and related nucleophiles
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"Chemical Equation Presented" A 1:1 mixture of [P(t-Bu) 2-obiphenyl]AuCl and AgSbF6 catalyzes the intermolecular amination of allylic alcohols with 1-methylimldazolidin-2one and related nucleophiles that, In the case of γ-unsubstituted or γ-methyl- substituted allylic alcohols, occurs with high γ-regioselectivity and syn-stereoselectivlty.
- Mukherjee, Paramita,Widenhoeferst, Ross A.
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supporting information; experimental part
p. 1184 - 1187
(2010/05/18)
-
- Amidation through carbamates
-
N-Alkyl carbamates of primary amines are easily converted into amides under treatment with Grignard reagents. Consequently, primary amines can be converted into amides in a one-pot reaction through carbamate protection and Grignard addition.
- Latorre, Antonio,Rodríguez, Santiago,Izquierdo, Javier,González, Florenci V.
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experimental part
p. 2653 - 2655
(2009/08/09)
-
- Scope and mechanism of formal SN2′ substitution reactions of a monomeric imidozirconium complex with allylic electrophiles
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The zirconium imido complex Cp2(THF)Zr=NSi(t-Bu)Me2 (1) reacts with allylic ethers, chlorides, and bromides to give exclusively the products of the SN2′ reaction; i.e., attack at the allylic position remote from the leavin
- Lalic, Gojko,Krinsky, Jamin L.,Bergman, Robert G.
-
p. 4459 - 4465
(2008/12/22)
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- Oxidative Mannich reaction of N-carbobenzyloxy amines with 1,3-dicarbonyl compounds
-
(Chemical Equation Presented) Efficient carbon-carbon bond formation at the α-position of nitrogen was established by one-pot oxidative Mannich reaction of N-carbobenzyloxy (Cbz) amines with 1,3-dicarbonyl compounds using N-tert-butylbenzenesulfinimidoyl chloride as an oxidant.
- Matsuo, Jun-Ichi,Tanaki, Yumi,Ishibashi, Hiroyuki
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p. 4371 - 4374
(2007/10/03)
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- Heteroaryl alkyl piperazine derivatives
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Novel compounds of the general formula: and pharmaceutically acceptable acid addition salts thereof, wherein the compounds are useful in therapy to protect skeletal muscles against damage resulting from trauma or to protect skeletal muscles subsequent to muscle or systemic diseases such as intermittent claudication, to treat shock conditions, to preserve donor tissue and organs used in transplants, in the treatment of diabetes, in the treatment of cardiovascular diseases including atrial and ventricular arrhythmias, Prinzmetal's (variant) angina, stable angina, and exercise induced angina, congestive heart disease, and myocardial infarction.
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-
-
- Zirconium-mediated SN2′ substitution of allylic ethers: Regio- and stereospecific formation of protected allylic amines
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A new zirconium-mediated, regio- and stereospecific SN2′ substitution of allylic ethers with a nitrogen nucleophile has been developed. Cbz-protected amine products were isolated in high yield from reactions with a wide range of Z allylic ether
- Lalic, Gojko,Blum, Suzanne A.,Bergman, Robert G.
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p. 16790 - 16791
(2007/10/03)
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- SUBSTITUTED HETEROCYCLIC COMPOUNDS
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Disclosed are novel piperazine derivatives, useful for the treatment of various disease states, in particular cardiovascular diseases such as atrial and ventricular arrhythmias, intermittent claudication, Prinzmetal's (variant) angina, stable and unsta
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-
-
- Heteroaryl alkyl piperazine derivatives
-
Novel compounds of the general formula: and pharmaceutically acceptable acid addition salts thereof, wherein the compounds are useful in therapy to protect skeletal muscles against damage resulting from trauma or to protect skeletal muscles subsequent to muscle or systemic diseases such as intermittent claudication, to treat shock conditions, to preserve donor tissue and organs used in transplants, in the treatment of cardiovascular diseases including atrial and ventricular arrhythmias, Prinzmetal's (variant) angina, stable angina, and exercise induced angina, congestive heart disease, and myocardial infarction.
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-
-
- Heteroaryl alkyl piperazine derivatives
-
Novel compounds of the general formula: and pharmaceutically acceptable acid addition salts thereof, wherein the compounds are useful in therapy to protect skeletal muscles against damage resulting from trauma or to protect skeletal muscles subsequent to muscle or systemic diseases such as intermittent claudication, to treat shock conditions, to preserve donor tissue and organs used in transplants, in the treatment of diabetes, in the treatment of cardiovascular diseases including atrial and ventricular arrhythmias, Prinzmetal's (variant) angina, stable angina, and exercise induced angina, congestive heart disease, and myocardial infarction.
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-
-
- Sulfonamide derivatives
-
The present invention relates to a compound of formula (I) or a pharmaceutically acceptable salt thereof which is useful for the treatment of conditions associated with glutamate hypofunction, such as psychiatric and neurological disorders
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-
-
- Photochemical protection of amines with Cbz and Fmoc groups
-
The photochemical conversion of amines into carbamates was achieved using N-Cbz-, N-Fmoc-, and N-Boc-5,7-dinitroindolines. This reaction allows the protection of amines in neutral medium. Primary and unhindered secondary amines were protected to yield their benzyloxycarbonyl- and 9-fluorenylmethoxycarbonyl derivatives efficiently, whereas bulky amines or anilines gave low yields or no product. On the other hand, the formation of N-Boc compounds, although possible, proceeded only with low yields.
- Helgen, Celine,Bochet, Christian G.
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p. 2483 - 2486
(2007/10/03)
-
- Monomeric building blocks for labeling peptide nucleic acids
-
The invention relates to novel monomeric building blocks for labeling peptide nucleic acids and similarly constructed nucleic acid-binding oligomers possessing groups which are coupled to a nitrogen base and/or to the peptide backbone of the peptide nucle
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-
-
- The reaction of amines with benzyl halides under CO2 atmosphere
-
To find a useful, practical, and ecologically safer way to synthesize protected amines, the reactions of amines with benzyl halides under CO2 atmosphere were systematically examined. For primary amines, the CO2-inserted products were obtained in higher yields in the presence of DBU as a base, under a high pressure of CO2, and in a low-polarity solvent (toluene/hexane 1:1). Secondary amines gave only low yields of CO2-inserted products.
- Shi,Shen
-
p. 3357 - 3365
(2007/10/03)
-
- Potent HIV protease inhibitors containing a novel (2-Phenylsulfanyl-1-Hydroxyethyl)amide isostere
-
Based on the concept of bioisosterism, we report the design and synthesis of new protease inhibitors. These new compounds incorporate in their backbone the synthon 2-N-Acyl-2-Phenylsulfanyl-1-Hydroxyethyl (I) which confers on the resulting compounds both
- Rocheblave,Priem,De Michelis,Kraus
-
p. 4173 - 4176
(2007/10/03)
-
- Role of the macrocyclic polyether in the synthesis of N-alkylcarbamate ester from primary amines, CO2 and alkyl halides in the presence of crown-ethers
-
Primary amines, RNH2 1, and CO2 easily afford monoalkylammonium N-alkylcarbamates, [RNH3][O2CNHR] 2, that have been reacted with alkyl halides, R'X, in the presence of crown-ethers to give organic carbamates in good yield. We report here the synthesis and spectroscopic characterization of some alkylammonium carbamates 2, where R - benzyl 2a, allyl 2b, ter-butyl 2c, cyclohexyl 2d, and discuss their stability in solution and the conditions in which they can react with alkyl halides to give organic carbamates, RNHC(O)OR'. The role played by the macrocyclic ligand in modifying the reactivity of monoalkylammonium carbamates 2 towards R'X has been rationalized and the influence of parameters such as solvent, temperature and CO2 pressure on the yield and selectivity of the process leading to organic carbamates has been also settled.
- Aresta,Quaranta
-
p. 1515 - 1530
(2007/10/02)
-
- Irreversible inactivation of papain and cathepsin B by epoxidic substrate analogues
-
Epoxidic substrate analogues related to allylamine (4a-4e) and allyl alcohol (5a-5f) were synthesized and tested as models of cysteine-protease inhibitors.They proved to be irreversible inhibitors of papain and cathepsin B with pseudo-first-order inactiva
- Giordano, C.,Gallina, C.,Consalvi, V.,Scandurra, R.
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p. 479 - 487
(2007/10/02)
-
- NITRILE OXIDES IN MEDICINAL CHEMISTRY-- 2. SYNTHESIS OF THE TWO ENANTIOMERS OF DIHYDROMUSCIMOL
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The cycloaddition of bromonitrile oxide to monosubstituted olefins has a high regioselectivity yielding 3-bomo-5-substituted isoxazolines contaminated by minor amounts (4-9percent) of the 4-substituted isomer.The adducts of bromonitrile oxide to allyl alcohol and N-protected allylamine were employed as key intermediates in the preparation of racemic dihydromuscimol (DHM).The synthesis of (R)-(-)- and (S)-(+)-DHM was accomplished by using the two diastereomers obtained by the cycloaddition of bromonitrile oxide to (S)-(+)-isopropylidene-3-buten-1,2-diol.The enantiomeric excess of R)-(-)- and (S)-(+)-DHM, determined by capillary GLC on the appropriate precursors, were 98.8 and >99.0 percent.A spectroscopic survey of the tautomerism of 3-hydroxyisoxazolines indicates the predominant or exclusive occurence of the NH form.
- Amici, Marco De,Micheli, Carlo De,Misani, Valeria
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p. 1975 - 1986
(2007/10/02)
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- Carboxy- and Cyano-Hydroxylation of Alkenes. - Synthesis of 3-Hydroxy-4-amino Acids and Butyrolactones via the Isoxazoline Route
-
Dichloro- and dibromoformaldoximes are useful 1,3-dipolar cycloaddition reagents.They are conveniently preparated in situ, in high yields by dihalogenation of glyoxalic acid aldoxime with N-bromo- and N-chlorosuccinimide or tert-butyl hypochlorite.Dehydrohalogenation with potassium hydrogen carbonate in the presence of alkenes gives 3-halo-isoxazolines in a one-pot reaction.Reduction with iron pentacarbonyl gives β-hydroxynitriles.Methoxylation and catalytic reduction give β-hydroxy esters.Allyl alcohols and allylamines are transformed with halonitrile oxides into butyrolactones (DL-angelica lactone) and DL-3-hydroxy-4-amino acids (carnitine, 4-amino-3-hydroxybutyric acid), respectively.The lactonization is best effected by heating the γ-silyloxy ester in acetic acid with potassium hydrogen sulfate as catalyst.A synthesis of N-Boc-dihydromuscimol is described.
- Halling, Karen,Thomsen, Ib,Torssell, Kurt B. G.
-
p. 985 - 990
(2007/10/02)
-
- Synthesis of Analogues of 1,3-Dihydroxyacetone Phosphate and Glyceraldehyde 3-Phosphate for Use in Studies of Fructose-1,6-diphosphate Aldolase
-
This paper describes the synthesis of five analogues of dihydroxyacetone phosphate (3-azidohydroxyacetone 1-phosphate (5), 3-(acetylamino)hydroxyacetone 1-phosphate (12), (R)-1,3-dihydroxy-2-butanone 1-phosphate (18), (+/-)-1,3-dihydroxy-2-butanone 3-phosphate (26), and phosphonomethyl glycolate (31)).The syntheses of 18 and 26 are based on a new reaction: that is, the introduction of the phosphate group by the reaction of a diazo ketone with dibenzyl phosphate.These methods provide easy access to a number of compounds that are potential substrates for the synthetically useful enzyme aldolase (fructose-1,6-diphosphate aldolase from rabbit muscle, EC 4.1.2.13, RAMA) and perhaps for other enzymes of glycolysis.This paper also describes syntheses of 14 aldehydes for examination as substrates for aldolase.When the precursor was available, ozonolysis of vinyl groups proved to be the best route to the corresponding aldehydes.
- Bischofberger, Norbert,Waldmann, Herbert,Saito, Tohru,Simon, Ethan S.,Lees, Watson,et al.
-
p. 3457 - 3465
(2007/10/02)
-
- Allylic Selenides in Organic Synthesis: New Methods for the Synthesis of Allylic Amines
-
Oxidative rearrangement of allylic selenides in the presence of various amine nucleophiles provides synthetic access to a variety of allylic amine derivatives.The stereochemical outcome of these reactions has been investigated, and is consistent with a -sigmatropic rearrangement mechanism.Several D-α-amino acids and racemic β,γ-unsaturated α-amino acids were prepared in this manner.A variant of this process employing an achiral allylic selenide and chiral amide afforded protected allylic amines in low diastereoisomeric excess.
- Shea, Regan G.,Fitzner, Jeffrey N.,Fankhauser, John E.,Spaltenstein, Andreas,Carpino, Philip A.,et al.
-
p. 5243 - 5252
(2007/10/02)
-
- Preparation of Protected Allylic Primary Amines from Allylic Phenyl Selenides
-
The reaction of an allylic selenide with an excess of an O-alkyl-N-chloro-N-sodiocarbamate in methanol affords an alkoxycarbonyl-protected allylic primary amine with allylic transposition.The preparation of several tert-butoxycarbonyl- and benzyloxycarbon
- Fitzner, Jeffrey N.,Shea, Reagan G.,Fankhauser, John E.k,Hopkins, Paul B.
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p. 605 - 612
(2007/10/02)
-