- Stereocontrolled synthesis of the enantiomers of 1-[2-hydroxy-3-(4-phenyl-1-piperazinyl)-propyl]-pyrrolidin-2-one
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The asymmetric synthesis of 1-[2-hydroxy-3-(4-phenyl-1-piperazinyl)-propyl]-pyrrolidin-2-one 1 is described. Enantiomers of compound 1 were obtained using the Sharpless asymmetric dihydroxylation (AD) or hydrolytic kinetic resolution (HKR) methods. The enantiomers of compound 1, which were obtained by HKR had higher enantiomeric excesses than those which were synthesized by AD and epoxidation. The enantiomeric purity of the synthesized compounds was determinated by capillary electrophoresis.
- Kulig, Katarzyna,Holzgrabe, Ulrike,Malawska, Barbara
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- Synthesis of 1,2-Aminoalcohols through Enantioselective Aminoallylation of Ketones by Cu-Catalyzed Reductive Coupling
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Herein, we report the development of a catalytic enantioselective addition of N-substituted allyl equivalents to ketone electrophiles through use of Cu-catalyzed reductive coupling to access important chiral 1,2-aminoalcohol synthons in high levels of regio-, diastereo-, and enantioselectivity. Factors affecting enantioinduction are discussed including the identification of a reversible ketone allylation step that has not been previously reported in Cu-catalyzed reductive coupling.
- Klake, Raphael K.,Edwards, Mytia D.,Sieber, Joshua D.
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- Isoxazoline, isoxazole, and oxadiazole derivatives as M1 muscarinic acetylcholine receptor agonists
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Insertion of a methylene linker between the 2-pyrrolidinone substituent and the isoxazoline core of the lead compound 1 previously reported resulted in the loss of its agonistic activity. One exception was the compound 6f having oxadiazole core and 2-azabicyclo[2.2.1]heptane substituent. Of the two isomers of 6f, exo-isomer (EC50 0.013 μM) was five-to six-fold more effective than endo-isomer (EC50 0.30 μM), and ca. two-fold active than the mother compound 1 (EC50 0.031 μM) in stimulating the M1 mAChR. Both isomers were moderately selective agonists for M1 mAChR over the rest four subtypes, and it could be explained by docking study on active conformation allosteric binding sites of M1-M5 mAChRs and calculating their binding energies.
- Muthusamy, Selvaraj,Lee, Soo Min,Huang, Minghua,Cho, Nam-Chul,Nam, Ghilsoo,Pae, Ae Nim,Rhim, Hyewhon,Keum, Gyochang,Choi, Kyung Il
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- Novel Pyrrolinium-based Ionic Liquids for Lithium Ion Batteries: Effect of the Cation on Physicochemical and Electrochemical Properties
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Lithium ion batteries (LIBs) are one of the most promising energy conversion/storage systems, but the low thermal stability of the current electrolytes in LIBs should be improved to expand their potential applications. To enhance the safety properties of LIBs, novel pyrrolinium-based ionic liquids (ILs) were proposed as an alternative electrolyte to the current carbonate electrolyte, which have some task-specific functional groups, i.e., a planar C[dbnd]N double bond, a C-O ether linkage, and no unstable C-H bond, designed to improve their electrochemical performances as well as the physicochemical properties. As a result, the pyrrolinium-based ILs exhibited much improved physicochemical and electrochemical properties compared to those of the known ILs. Among the prepared ILs, N-allyl-2-methoxypyrrolinium bis(fluorosulfonyl)imide (A(OMe)Pyrl-FSI, 4) showed the high ionic conductivity (10.2 mS cm?1), the very good cycling performance (99.3% of retention ratio after 50 cycles) with a LiFePO4 electrode, and the much improved lithium ion transference number (0.19). IL 4 also had the remarkable rate capability at 5 C-rate with the retention ratio of 81.2% (124.8 mA h g?1), compared to the initial discharge capacity of 153.7 mA h g?1 at 0.1 C-rate. In addition, both their high thermal stability and non-flammability were also confirmed.
- Kim, Hyung-Tae,Kwon, Oh Min,Mun, Junyoung,Oh, Seung M.,Yim, Taeeun,Kim, Young Gyu
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- Thermally induced substrate release via intramolecular cyclizations of Amino esters and Amino carbonates
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The relative cleavage of an alcohol from a panel of amino esters and amino carbonates via intramolecular cyclization was examined as a mechanism for substrate release. Thermal stability at 37 °C was observed only for the seven-membered ring progenitors. Applicability of the approach was illustrated by δ-lactam formation within a poly(dimethylsiloxane) microchannel for release of a captured fluorescent probe.
- Knipp, Ralph J.,Estrada, Rosendo,Sethu, Palaniappan,Nantz, Michael H.
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supporting information
p. 3422 - 3429
(2014/05/06)
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- Radiosynthesis of 11C-levetiracetam: A potential marker for PET imaging of SV2A expression
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The multistep preparation of 11C-levetiracetam (11C-LEV) was carried out by a one-pot radiosynthesis with 8.3 ± 1.6% (n = 8) radiochemical yield in 50 ± 5.0 min. Briefly, the propionaldehyde was converted to propan-1-imine in situ as labeling precursor by incubation with ammonia. Without further separation, the imine was reacted with 11C-HCN to form 11C-aminonitrile. This crude was then reacted with 4-chlorobutyryl chloride and followed by hydrolysis to yield 11C-LEV after purification by chiral high-performance liquid chromatography (HPLC). Both the radiochemical and enantiomeric purities of 11C-LEV were >98%.
- Cai, Hancheng,Mangner, Thomas J.,Muzik, Otto,Wang, Ming-Wei,Chugani, Diane C.,Chugani, Harry T.
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supporting information
p. 1152 - 1155
(2014/12/10)
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- [Pd(μ-Br)(PtBu3)]2 as a highly active isomerization catalyst: Synthesis of enol esters from allylic esters
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The dimeric Pd(I)-complex [Pd(μ-Br)(PtBu3)] 2 was found to be highly active for catalyzing double-bond migration in various substrates such as unsaturated ethers, alcohols, amides, and arenes, under mild conditions. It efficiently mediates the conversion of allylic esters into enol esters, rather than inserting into the allylic C-O bond. The broad applicability of this reaction was demonstrated with the synthesis of 22 functionalized enol esters.
- Mamone, Patrizia,Gruenberg, Matthias F.,Fromm, Andreas,Khan, Bilal A.,Goossen, Lukas J.
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supporting information; experimental part
p. 3716 - 3719
(2012/09/08)
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- REVERSE HEAD GROUP LIPIDS, LIPID PARTICLE COMPOSITIONS COMPRISING REVERSE HEADGROUP LIPIDS, AND METHODS FOR THE DELIVERY OF NUCLEIC ACIDS
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The present invention related to a novel class of zwitterionic lipids that are useful in the preparation of lipid particles suitable for the delivery of encapsulated nucleic acids to cells.
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Page/Page column 33
(2011/06/11)
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- Catalytic, asymmetric vinylogous Mukaiyama aldol reactions of pyrrole- and furan-based dienoxy silanes: How the diene heteroatom impacts stereocontrol
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Denmark's chiral bisphosphoramide/silicon tetrachloride system performs as an excellent Lewis base-Lewis acid catalyst for the vinylogous Mukaiyama aldol reaction of pyrrole- and furan-based dienoxy silanes with aromatic and heteroaromatic aldehydes. This asymmetric methodology provides a powerful synthetic entry to a variety of d-hydroxylated g-butenolide-type frameworks with high efficiency and valuable margins of regio-, diastereo-, and enantioselectivity. Notably, the nature of the heteroatom within the vinylogous dienoxy silane donor heavily impacts the diastereocontrol, with syn-configured aldol adducts emerging from pyrroles bearing electron- withdrawing N-protecting groups (Boc, Ts, and Cbz) and anti-configured adducts prevailing when furan- or N-alkyl/alkenylpyrrole donors are involved.
- Curti, Claudio,Ranieri, Beatrice,Battistini, Lucia,Rassu, Gloria,Zambrano, Vincenzo,Pelosi, Giorgio,Casiraghi, Giovanni,Zanardi, Franca
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supporting information; experimental part
p. 2011 - 2022
(2010/11/17)
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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)
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- Synthesis of spirocyclic carbazole- and acridine-lactams
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Spirocyclic carbazole- and acridine-lactams were prepared by Fischer-indole or Friedlaender-quinoline synthesis starting from spirocyclic ketones with a lactam ring. All annulation products were obtained as mixtures of separable regioisomers, which differ only in the position of one methyl group. The starting materials were prepared from 2-pyrrolidone and 2-piperidone by a sequence of protection (by N-allylation), α-acylation, iron-catalyzed Michael reaction followed by Robinson-annulation, palladium-catalyzed N-deprotection and catalytic hydrogenation. The overall yields of this six-step sequence are 13 and 17%, respectively, and the racemic ketones are obtained as single diastereoisomers.
- Wuerdemann, Martina,Christoffers, Jens
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experimental part
p. 1894 - 1898
(2010/08/06)
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- Hydrolytic deallylation of N-allyl amides catalyzed by PdII complexes
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Hydrolytic deallylation of N-allyl amides to give amides and propanal can be achieved with PdII catalysts. The optimized catalyst consists of Pd(OCOCF3)2 and 1,3-bis(diphenylphosphanyl) propane (DPPP). Several kinds of open-chain N-allyl amides and N-allyl lactams undergo hydrolytic deallylation to give the corresponding amides and lactams in good to high yield. A mechanism which includes isomerization to enamides and subsequent hydrolysis is proposed. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.
- Ohmura, Naoya,Nakamura, Asami,Hamasaki, Akiyuki,Tokunaga, Makoto
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supporting information; experimental part
p. 5042 - 5045
(2009/05/07)
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- A practical ruthenium-catalyzed cleavage of the allyl protecting group in amides, lactams, imides, and congeners
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A convenient methodology for the deprotection of N-allylic amide-like moieties was developed. The first examples accounting for the ruthenium-catalyzed deallylation of amides, lactams, imides, pyrazolidones, hydantoins, and oxazolidinones have been achieved by the sequential use of Grubbs carbene (isomerization step) and RuCl3 (oxidation step). A variety of substrates, including enantiopure multifunctional β- and γ-lactams, can be employed.
- Alcaide, Benito,Almendros, Pedro,Alonso, Jose M.
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p. 2874 - 2879
(2008/02/03)
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- A new highly chemoselective isomerization of allylamides
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This work describes the first iridium-catalyzed isomerization of N-allylamides into enamides. This strategy allows the chemoselective preparation of (E)-N-(1-propenyl)-enamides and can be applied for the selective deprotection of N-allylamides.
- Neugnot, Benjamin,Cintrat, Jean-Christophe,Rousseau, Bernard
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p. 3575 - 3579
(2007/10/03)
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- Organic polymers and novel polymerizable compound
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Organic polymers having water contact angles of 20° or smaller, preferably 7° or smaller and equipped with both high wettability and high transparency. The organic polymers may contain as partial structures polar structures of about 3 debyes or higher in dipole moment and are available especially from polymerization of polymerizable compounds having alkylene(thio)urea structures.
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- Pyrrolidinone derivatives, their preparation and pharmaceutical composition comprising the same
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The present invention relates to substituted pyrrolidinone compounds of formula 1, wherein n is 0 or 1; Aza is a heterocycle optionally substituted with C1-4 alkyl, or C1-4 alkyl substituted with a heterocycle, which represents a saturated or unsaturated five- or six-membered ring having nitrogen(s) as a heteroatom, which are muscarinic acetylcholine receptor agonists and useful as nootropics and therapeutic agents for cerebral neural diseases such as Alzheimer's disease; and pharmaceutically acceptable salts thereof; processes for the preparation thereof; and pharmaceutical compositions comprising these compounds or salts.
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- Palladium-catalyzed aminoallylation of activated olefins with allylic halides and phthalimide
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The three-component aminoallylation reaction of the activated olefins 2 with the phthalimide 1a and allyl chloride proceeded very smoothly in the presence of Pd2dba3·CHCl3 (5 mol %)/P(4-FC6H4)3 (40 mol %) and Cs2CO3 (3 equiv against 2) in dichloromethane at room temperature to give the corresponding aminoallylated products, N-pent-4-enylphthalimides 3, in 58-99% yields. The reaction of oxazolidinone 1b also proceeded very smoothly to give N-(2,2-dicyano-1-phenylpent-4-enyl)-oxazolidinone in a quantitative yield; however, the Tsuji-Trost-type allylation products 4 were obtained in the case of dibenzylamine, N-tosylaniline, and pyrrolidin-2-one. Further, 2 underwent cycloaddition with N-tosylvinylaziridine 9a in the presence of Pd2dba3·CHCl3 (5 mol %)/P(4-FC6H4)3 (40 mol %) in THF at room temperature, giving the corresponding pyrrolidines 11 in 69-99% yields.
- Aoyagi, Kouichi,Nakamura, Hiroyuki,Yamamoto, Yoshinori
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p. 5977 - 5980
(2007/10/03)
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- Synthesis of Pyrrolidines and Pyrrolidinones by the Rhodium Complex Catalyzed Cyclization of Unsaturated Amines
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N-Allylic arylamines react with carbon monoxide, sodium borohydride, 2-propanol, and catalytic amounts of the zwitterionic complex η6-C6H6BPh3-Rh(COD)+ (1), to form pyrrolidines as the main products in most cases.Pyrrolidinones result from N-allylic alkylamines.An alternate route to the lactams from N-allylic alkylamines involves synthesis gas instead of CO/NaBH4, together with the dual catalytic system 1/2.Complementary to the N-allylic arylamine route to pyrrolidines with NaBH4 and 1 is the use of synthesis gas, 1, and 1,4-bis(diphenylphosphino)butane.
- Zhou, Jian-Qiang,Alper, Howard
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p. 3328 - 3331
(2007/10/02)
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- 3-(2-oxo-1-pyrrolidinyl)-propylsilanes and method for preparing the silane compounds
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3-(2-oxo-1-pyrrolidinyl)-propylsilane compounds represented by the following general formula (I) are herein disclosed: STR1 wherein R1 and R2 may be the same or different and each represents a hydrocarbon group having 1 to 4 carbon atoms; and n is an integer ranging from 0 to 2. The propylsilane compounds may be prepared by, for instance, reacting 1-allyl-2-oxopyrrolidine with a hydrogen silane such as trimethoxysilane or trichlorosilane in the presence of a platinum catalyst or further optionally reacting the resulting 3-(2-oxo-1-pyrrolidinyl)-propyl halogenosilane (in the case where a halogenosilane is used) with an alcohol such as methanol. These propylsilane compounds are effective as anti-clouding agent for treating the surface of a variety of substrate.
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- DI- OR TRIPEPTIDE RENIN INHIBITORS CONTAINING LACTAM CONFORMATIONAL RESTRICTION IN ACHPA
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Enzyme di-or tripeptides of the formula: STR1 and analogs thereof which inhibit renin and are useful for treating various forms of renin-associated hypertension, hyperaldosteronism and congestive heart failure; compositions containing these renin-inhibitory peptides, optionally with other antihypertensive agents; and methods of treating hypertension, hyperaldosteronism or congestive heart failure or of establishing renin as a causative factor in these problems which employ these novel peptides.
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- EFFICIENT SYNTHESIS OF N-SUBSTITUTED LACTAMS FROM (N-ARYLSULFONYLOXY)AMINES AND CYCLIC KETONES
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A new method is reported for the direct preparation of N-substituted lactams from cycloalkanones.N-(p-nitrobenzenesulfonoxyl) methylamine 1a (CH3NH-OSO2C6H4NO2) was reacted with a series of cycloalkanones to give good yields of N-methyl lactams.An addition-rearrangement pathway accounts for the ring-expanded lactam products.A series of N-alkyl-N-arylsulfonoxyl amines were generated in situ and reacted with cyclobutanone to give N-alkyl pyrrolidinones in high yields.
- Hoffman, Robert V.,Salvador, James M.
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p. 4207 - 4210
(2007/10/02)
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- CARBONYL RADICAL CYCLIZATIONS: PREPARATION OF SOME HETEROCYCLIC KETONES
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It has been possible to synthesize 3-methylchromanone, 3-methylthiochromanone and 2,3-dihydro-3-methylquinolin-4-one from salicylic acid, thiosalicylic acid and anthranilic acid respectively by carbonyl radical cyclizations.
- Crich, David,Eustace, K. Angeline,Ritchie, Timothy J.
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- Direct N-Allylation of Amides with 2-Allylisourea Catalyzed by Palladium(0)
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Direct N-allylation of amides catalyzed by palladium(0) complexes took place under neutral conditions by the use of 2-allylisourea as the allylating agent.
- Inoue, Yoshio,Taguchi, Masaaki,Hashimoto, Harukichi
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p. 2721 - 2722
(2007/10/02)
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- Pyrrolizidinone and Indolizidinone Synthesis: Generation and Intramolecular Addition of α-Acylamino Radicals to Olefins and Allenes
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α-Acylamino radicals can be generated by treatment of phenylthio, methylthio, or phenylselenyl lactams of type 7, 8, and 17 with tri-n-butyltin hydride in the presence of AIBN.The radicals add intramolecularly to olefins and allenes to give indolizidinones and pyrrolizidinones.The product distribution depends on the substitution patterns of the unsaturated moiety and the legnth of the chain connecting the radical and olefinic centers.Product ratios appear to reflect the kinetic partitioning of the radical between cyclization pathways.These reactions are potentially useful in the area of pyrrolizidine alkaloid synthesis.The conversion of cyclization produts 50 and 51 to (+/-)-supinidine (1) serves as an example.
- Burnett, Duane A.,Choi, Joong-Kwon,Hart, David J.,Tsai, Yeun-Min
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p. 8201 - 8209
(2007/10/02)
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