- THE MECHANISM OF PHOTOREDUCTION OF CYCLOHEXENONES TO CYCLOHEXANONES IN ISOPROPYL ALCOHOL
-
The photoreduction of cyclohexenones in 2-propanol is initiated by H-abstraction at Cβ of the enone 3?,?* state, as shown by the reaction course in deuterated solvents.
- Schuster, David I.,Nunez, Ivan M.,Chan, Chung B.
-
-
Read Online
- Photocontrolled Cobalt Catalysis for Selective Hydroboration of α,β-Unsaturated Ketones
-
Selectivity between 1,2 and 1,4 addition of a nucleophile to an α,β-unsaturated carbonyl compound has classically been modified by the addition of stoichiometric additives to the substrate or reagent to increase their “hard” or “soft” character. Here, we demonstrate a conceptually distinct approach that instead relies on controlling the coordination sphere of a catalyst with visible light. In this way, we bias the reaction down two divergent pathways, giving contrasting products in the catalytic hydroboration of α,β-unsaturated ketones. This includes direct access to previously elusive cyclic enolborates, via 1,4-selective hydroboration, providing a straightforward and stereoselective route to rare syn-aldol products in one-pot. DFT calculations and mechanistic experiments confirm two different mechanisms are operative, underpinning this unusual photocontrolled selectivity switch.
- Beltran, Frédéric,Bergamaschi, Enrico,Funes-Ardoiz, Ignacio,Teskey, Christopher J.
-
p. 21176 - 21182
(2020/09/17)
-
- Iron-catalyzed oxidative functionalization of C(sp3)-H bonds under bromide-synergized mild conditions
-
An efficient oxidation and functionalization of C-H bonds with an inorganic-ligand supported iron catalyst and hydrogen peroxide to prepare the corresponding ketones was achieved using the bromide ion as a promoter. Preliminary mechanistic investigations indicated that the bromide ion can bind to FeMo6 to form a supramolecular species (FeMo6·2Br), which can effectively catalyze the reaction.
- Yu, Han,Zhao, Qixin,Wei, Zheyu,Wu, Zhikang,Li, Qi,Han, Sheng,Wei, Yongge
-
supporting information
p. 7840 - 7843
(2019/07/12)
-
- Iridium-Catalyzed Alkene-Selective Transfer Hydrogenation with 1,4-Dioxane as Hydrogen Donor
-
The iridium-catalyzed transfer hydrogenation of alkenes using 1,4-dioxane as a hydrogen donor is described. The use of 1,2-bis(dicyclohexylphosphino)ethane (DCyPE), featuring bulky and highly electron-donating properties, led to high catalytic activity. A polystyrene-cross-linking bisphosphine PS-DPPBz produced a reusable heterogeneous catalyst. These homogeneous and heterogeneous protocols achieved chemoselective transfer hydrogenation of alkenes over other potentially reducible functional groups such as carbonyl, nitro, cyano, and imino groups in the same molecule.
- Zhang, Deliang,Iwai, Tomohiro,Sawamura, Masaya
-
supporting information
p. 5867 - 5872
(2019/08/26)
-
- Catalyst-controlled aliphatic C—H oxidations
-
The invention provides simple small molecule, non-heme iron catalyst systems with broad substrate scope that can predictably enhance or overturn a substrate's inherent reactivity preference for sp3-hybridized C—H bond oxidation. The invention also provides methods for selective aliphatic C—H bond oxidation. Furthermore, a structure-based catalyst reactivity model is disclosed that quantitatively correlates the innate physical properties of the substrate to the site-selectivities observed as a function of the catalyst. The catalyst systems can be used in combination with oxidants such as hydrogen peroxide to effect highly selective oxidations of unactivated sp3 C—H bonds over a broad range of substrates.
- -
-
Page/Page column 36-37; 47-48
(2018/04/20)
-
- General, Simple, and Chemoselective Catalysts for the Isomerization of Allylic Alcohols: The Importance of the Halide Ligand
-
Remarkably simple IrIIIcatalysts enable the isomerization of primary and sec-allylic alcohols under very mild reaction conditions. X-ray absorption spectroscopy (XAS) and mass spectrometry (MS) studies indicate that the catalysts, with the general formula [Cp*IrIII], require a halide ligand for catalytic activity, but no additives or additional ligands are needed.
- Erbing, Elis,Vázquez-Romero, Ana,Bermejo Gómez, Antonio,Platero-Prats, Ana E.,Carson, Fabian,Zou, Xiaodong,Tolstoy, P?ivi,Martín-Matute, Belén
-
supporting information
p. 15659 - 15663
(2016/10/25)
-
- Readily Accessible Bulky Iron Catalysts exhibiting Site Selectivity in the Oxidation of Steroidal Substrates
-
Bulky iron complexes are described that catalyze the site-selective oxidation of alkyl C-H bonds with hydrogen peroxide under mild conditions. Steric bulk at the iron center is introduced by appending trialkylsilyl groups at the meta-position of the pyridines in tetradentate aminopyridine ligands, and this effect translates into high product yields, an enhanced preferential oxidation of secondary over tertiary C-H bonds, and the ability to perform site-selective oxidation of methylenic sites in terpenoid and steroidal substrates. Unprecedented site selective oxidation at C6 and C12 methylenic sites in steroidal substrates is shown to be governed by the chirality of the catalysts.
- Font, David,Canta, Mercè,Milan, Michela,Cussó, Olaf,Ribas, Xavi,Klein Gebbink, Robertus J. M.,Costas, Miquel
-
supporting information
p. 5776 - 5779
(2016/05/09)
-
- Bis-Michael Acceptors as Novel Probes to Study the Keap1/Nrf2/ARE Pathway
-
Nuclear factor erythroid 2-related factor 2 (Nrf2) is a master regulator that promotes the transcription of cytoprotective genes in response to oxidative/electrophilic stress. Various Michael-type compounds were designed and synthesized, and their potency
- Deny, Ludovic J.,Traboulsi, Hussein,Cantin, André M.,Marsault, éric,Richter, Martin V.,Bélanger, Guillaume
-
p. 9431 - 9442
(2016/11/11)
-
- As opioid receptor antagonists or inverse agonists of the novel compounds
-
Novel compounds which are antagonists or inverse agonists at one or more of the opioid receptors, pharmaceutical compositions containing them, to processes for their preparation.
- -
-
Paragraph 0231; 0232
(2016/10/08)
-
- Trapping a Highly Reactive Nonheme Iron Intermediate That Oxygenates Strong C-H Bonds with Stereoretention
-
An unprecedentedly reactive iron species (2) has been generated by reaction of excess peracetic acid with a mononuclear iron complex [FeII(CF3SO3)2(PyNMe3)] (1) at cryogenic temperatures, and characterized spectroscopically. Compound 2 is kinetically competent for breaking strong C-H bonds of alkanes (BDE ≈ 100 kcal·mol-1) through a hydrogen-atom transfer mechanism, and the transformations proceed with stereoretention and regioselectively, responding to bond strength, as well as to steric and polar effects. Bimolecular reaction rates are at least an order of magnitude faster than those of the most reactive synthetic high-valent nonheme oxoiron species described to date. EPR studies in tandem with kinetic analysis show that the 490 nm chromophore of 2 is associated with two S = 1/2 species in rapid equilibrium. The minor component 2a (~5% iron) has g-values at 2.20, 2.19, and 1.99 characteristic of a low-spin iron(III) center, and it is assigned as [FeIII(OOAc)(PyNMe3)]2+, also by comparison with the EPR parameters of the structurally characterized hydroxamate analogue [FeIII(tBuCON(H)O)(PyNMe3)]2+ (4). The major component 2b (~40% iron, g-values = 2.07, 2.01, 1.95) has unusual EPR parameters, and it is proposed to be [FeV(O)(OAc)(PyNMe3)]2+, where the O-O bond in 2a has been broken. Consistent with this assignment, 2b undergoes exchange of its acetate ligand with CD3CO2D and very rapidly reacts with olefins to produce the corresponding cis-1,2-hydroxoacetate product. Therefore, this work constitutes the first example where a synthetic nonheme iron species responsible for stereospecific and site selective C-H hydroxylation is spectroscopically trapped, and its catalytic reactivity against C-H bonds can be directly interrogated by kinetic methods. The accumulated evidence indicates that 2 consists mainly of an extraordinarily reactive [FeV(O)(OAc)(PyNMe3)]2+ (2b) species capable of hydroxylating unactivated alkyl C-H bonds with stereoretention in a rapid and site-selective manner, and that exists in fast equilibrium with its [FeIII(OOAc)(PyNMe3)]2+ precursor.
- Serrano-Plana, Joan,Oloo, Williamson N.,Acosta-Rueda, Laura,Meier, Katlyn K.,Verdejo, Bego?a,García-Espa?a, Enrique,Basallote, Manuel G.,Münck, Eckard,Que, Lawrence,Company, Anna,Costas, Miquel
-
supporting information
p. 15833 - 15842
(2016/01/09)
-
- The iron(II) complex [Fe(CF3SO3)2(mcp)] as a convenient, readily available catalyst for the selective oxidation of methylenic sites in alkanes
-
The efficient and selective oxidation of secondary C-H sites of alkanes is achieved by using low catalyst loadings of a non-expensive, readily available iron catalyst [Fe(II)(CF3SO3)2(mcp)], {Fe-mcp, [mcp=N,N'-dimethyl-N,N'-bis(2-pyridylmethyl)cyclohexane-trans-1,2-diamine]}, and hydrogen peroxide (H2O2) as oxidant, via a simple reaction protocol. Natural products are selectively oxidized and isolated in synthetically amenable yields. The easy access to large quantities of the catalyst and the simplicity of the C-H oxidation procedure make this system a particularly convenient tool to carry out alkane C-H oxidation reactions on the preparative scale, and in short reaction times.
- Canta, Merce,Font, David,Gomez, Laura,Ribas, Xavi,Costas, Miquel
-
supporting information
p. 818 - 830
(2014/04/03)
-
- Novel S1P1 receptor agonists - Part 2: From bicyclo[3.1.0] hexane-fused thiophenes to isobutyl substituted thiophenes
-
Previously, we reported on the discovery of a novel series of bicyclo[3.1.0]hexane fused thiophene derivatives that serve as potent and selective S1P1 receptor agonists. Here, we discuss our efforts to simplify the bicyclohexane fused thiophene
- Bolli, Martin H.,Velker, J?rg,Müller, Claus,Mathys, Boris,Birker, Magdalena,Bravo, Roberto,Bur, Daniel,De Kanter, Ruben,Hess, Patrick,Kohl, Christopher,Lehmann, David,Meyer, Solange,Nayler, Oliver,Rey, Markus,Scherz, Michael,Steiner, Beat
-
-
- C-H oxidation by H2O2 and O2 catalyzed by a non-heme iron complex with a sterically encumbered tetradentate N-donor ligand
-
The compound N,N′-dineopentyl-N,N′-bis(2-pyridylmethyl)-1,2- ethanediamine (dnbpn) and its ferrous complex [Fe(dnbpn)(OTf)2] were synthesized. The Fe(II) complex was used to catalyze the oxidation of hydrocarbons by H2O2 and O2. Although the catalyzed alkane oxidation by H2O2 displays a higher preference for secondary over tertiary carbons than those associated with most previously reported nonheme iron catalysts, the catalytic activity is markedly inferior. In addition to directing the catalyzed oxidation toward the less sterically congested C-H bonds of the substrates, the neopentyl groups destabilize the metal-based oxidants generated from H2O2 and the Fe(II) complex. The presence of benzylic substrates with weak C-H bonds stabilizes an intermediate which we have tentatively assigned as a high-spin ferric hydroperoxide species. The oxidant generated from O2 reacts with allylic and benzylic C-H bonds in the absence of a sacrificial reductant; less substrate dehydrogenation is observed than with related previously described systems that use O2 as a terminal oxidant.
- Zhang, Qiao,Gorden, John D.,Goldsmith, Christian R.
-
p. 13546 - 13554
(2014/01/06)
-
- Catalyst-controlled aliphatic c-h oxidations with a predictive model for site-selectivity
-
Selective aliphatic C-H bond oxidations may have a profound impact on synthesis because these bonds exist across all classes of organic molecules. Central to this goal are catalysts with broad substrate scope (small-molecule-like) that predictably enhance or overturn the substrate's inherent reactivity preference for oxidation (enzyme-like). We report a simple small-molecule, non-heme iron catalyst that achieves predictable catalyst-controlled site-selectivity in preparative yields over a range of topologically diverse substrates. A catalyst reactivity model quantitatively correlates the innate physical properties of the substrate to the site-selectivities observed as a function of the catalyst.
- Gormisky, Paul E.,White, M. Christina
-
supporting information
p. 14052 - 14055
(2013/10/21)
-
- Site-selective oxidation of unactivated C sp 3-H bonds with hypervalent iodine(III) reagents
-
By design: The site-selective oxidation of unactivated secondary C sp 3-H bonds was accomplished with hypervalent iodine(III) reagents and tert-butyl hydroperoxide (see scheme). The preparation and derivatization of the hypervalent iodine(III) reagent are simple, thus allowing the rational design of these reagents to optimize the site selectivity of the oxidation. Copyright
- Moteki, Shin A.,Usui, Asuka,Zhang, Tiexin,Solorio Alvarado, Cesar R.,Maruoka, Keiji
-
supporting information
p. 8657 - 8660
(2013/09/12)
-
- Regioselective oxidation of nonactivated alkyl C-H groups using highly structured non-heme iron catalysts
-
Selective oxidation of alkyl C-H groups constitutes one of the highest challenges in organic synthesis. In this work, we show that mononuclear iron coordination complexes Λ-[Fe(CF3SO3) 2((S,S,R)-MCPP)] (Λ-1P), Δ-[Fe(CF3SO 3)2((R,R,R)-MCPP)] (Δ-1P), Λ-[Fe(CF 3SO3)2((S,S,R)-BPBPP)] (Λ-2P), and Δ-[Fe(CF3SO3)2((R,R,R)-BPBPP)] (Δ-2P) catalyze the fast, efficient, and selective oxidation of nonactivated alkyl C-H groups employing H2O2 as terminal oxidant. These complexes are based on tetradentate N-based ligands and contain iron centers embedded in highly structured coordination sites defined by two bulky 4,5-pinenopyridine donor ligands, a chiral diamine ligand backbone, and chirality at the metal (Λ or Δ). X-ray diffraction analysis shows that in Λ-1P and Λ-2P the pinene rings create cavity-like structures that isolate the iron site. The efficiency and regioselectivity in catalytic C-H oxidation reactions of these structurally rich complexes has been compared with those of Λ-[Fe(CF3SO3) 2((S,S)-MCP)] (Λ-1), Λ-[Fe(CF3SO 3)2((S,S)-BPBP)] (Λ-2), Δ-[Fe(CF 3SO3)2((R,R)-BPBP)] (Δ-2), Λ-[Fe(CH3CN)2((S,S)-BPBP)](SbF6) 2 (Λ-2SbF6), and Δ-[Fe(CH3CN) 2((R,R)-BPBP)](SbF6)2 (Δ-2SbF 6), which lack the steric bulk introduced by the pinene rings. Cavity-containing complexes Λ-1P and Λ-2P exhibit enhanced activity in comparison with Δ-1P, Δ-2P, Λ-1, Λ-2, and Λ-2SbF6. The regioselectivity exhibited by catalysts Λ-1P, Λ-2P, Δ-1P, and Δ-2P in the C-H oxidation of simple organic molecules can be predicted on the basis of the innate properties of the distinct C-H groups of the substrate. However, in specific complex organic molecules where oxidation of multiple C-H sites is competitive, the highly elaborate structure of the catalysts allows modulation of C-H regioselectivity between the oxidation of tertiary and secondary C-H groups and also among multiple methylene sites, providing oxidation products in synthetically valuable yields. These selectivities complement those accomplished with structurally simpler oxidants, including non-heme iron catalysts Λ-2 and Λ-2SbF6.
- Gómez, Laura,Canta, Merceì,Font, David,Prat, Irene,Ribas, Xavi,Costas, Miquel
-
p. 1421 - 1433
(2013/03/29)
-
- An iron catalyst for oxidation of alkyl C-H bonds showing enhanced selectivity for methylenic sites
-
Many are called but few are chosen: A nonheme iron complex catalyzes the oxidation of alkyl C-H bonds by using H2O2 as the oxidant, showing an enhanced selectivity for secondary over tertiary C-H bonds (see scheme). Copyright
- Prat, Irene,Gomez, Laura,Canta, Merce,Ribas, Xavi,Costas, Miquel
-
supporting information
p. 1908 - 1913
(2013/03/14)
-
- Graphene-supported Pd nanoparticles: Microwave-assisted synthesis and as microwave-active selective hydrogenation catalysts
-
Facile synthesis of graphene-supported Pd nanoparticles (NPs) with an average size of 5 nm (Pd/G) was achieved by a microwave-assisted reduction approach; the obtained Pd/G can be very effectively coupled to the microwave field, making it a high-performance catalyst (with turnover frequency (TOF) of 158 465 h-1) for microwave-assisted selective hydrogenation of isophorone at low temperatures. The Royal Society of Chemistry 2013.
- Yang, Jing-He,Ma, Ding
-
p. 10131 - 10134
(2013/09/02)
-
- COMPOUNDS FOR TREATING NEURODEGENERATIVE DISEASES
-
The invention provides novel spirotetrahydronaphthalene compounds of Formula α that inhibit β-secretase cleavage of APP and are useful as therapeutic agents for treating neurodegenerative diseases.
- -
-
Page/Page column 70-71
(2011/10/13)
-
- NOVEL COMPOUNDS AS ANTAGONISTS OR INVERSE AGONISTS AT OPIOID RECEPTORS
-
Novel compounds which are antagonists or inverse agonists at one or more of the opioid receptors, pharmaceutical compositions containing them, to processes for their preparation.
- -
-
-
- Azepanone-based inhibitors of human cathepsin S: Optimization of selectivity via the P2 substituent
-
A series of azepanone inhibitors of cathepsin S is described. Selectivity over both cathepsin K and cathepsin L was achieved by varying the P2 substituent. Ultimately, a balanced potency and selectivity profile was achieved in compound 39 possessing a 1-methylcyclohexyl alanine at P2 and nicotinamide as the P′ substituent. The cellular potency of selected analogs is also described.
- Kerns, Jeffrey K.,Nie, Hong,Bondinell, William,Widdowson, Katherine L.,Yamashita, Dennis S.,Rahman, Attiq,Podolin, Patricia L.,Carpenter, Donald C.,Jin, Qi,Riflade, Benoit,Dong, Xiaoyang,Nevins, Neysa,Keller, Paul M.,Mitchell, Laura,Tomaszek, Thaddeus
-
scheme or table
p. 4409 - 4415
(2011/09/15)
-
- Combined effects on selectivity in Fe-catalyzed methylene oxidation
-
Methylene C-H bonds are among the most difficult chemical bonds to selectively functionalize because of their abundance in organic structures and inertness to most chemical reagents. Their selective oxidations in biosynthetic pathways underscore the power of such reactions for streamlining the synthesis of molecules with complex oxygenation patterns. We report that an iron catalyst can achieve methylene C-H bond oxidations in diverse natural-product settings with predictable and high chemo-, site-, and even diastereoselectivities. Electronic, steric, and stereoelectronic factors, which individually promote selectivity with this catalyst, are demonstrated to be powerful control elements when operating in combination in complex molecules. This small-molecule catalyst displays site selectivities complementary to those attained through enzymatic catalysis.
- Chen, Mark S.,White, M. Christina
-
scheme or table
p. 533 - 571
(2010/10/05)
-
- MELANOCORTIN RECEPTOR AGONISTS
-
The present invention relates to a compound having a good agonistic activity to melanocortin receptor, or pharmaceutically acceptable salt or isomer thereof, and an agonistic composition for melanocortin receptor comprising the same as an active ingredient.
- -
-
Page/Page column 10
(2010/06/11)
-
- MELANOCORTIN RECEPTOR AGONISTS
-
The present invention relates to a compound having a good agonistic activity to melanocortin receptor, or pharmaceutically acceptable salt or isomer thereof, and an agonistic composition for melanocortin receptor comprising the same as an active ingredient.
- -
-
Page/Page column 23
(2010/06/15)
-
- SUBSTITUTED DIHYDRO AND TETRAHYDRO OXAZOLOPYRIMIDINONES, PREPARATION AND USE THEREOF
-
The present invention relates to a series of substituted dihydro and tetrahydro oxazolopyrimidinones, specifically, to a series of 2-substituted-2,3-dihydro-oxazolo[3,2-a]pyrimidin-7-ones and 2-substituted-2,3,5,6-tetra-hydro-oxazolo[3,2-a]pyrimidin-7-ones of formula (I): Wherein p, n, X, Y, R1, R2, R3, R4, R5, R6, R7 and R8 are as defined herein. This invention also relates to methods of making these compounds including novel intermediates. The compounds of this invention are modulators of metabotropic glutamate receptors (mGluR), particularly, mGluR2 receptor. Therefore, the compounds of this invention are useful as pharmaceutical agents, especially in the treatment and/or prevention of a variety of central nervous system disorders (CNS), including but not limited to acute and chronic neurodegenerative conditions, psychoses, convulsions, anxiety, depression, migraine, pain, sleep disorders and emesis.
- -
-
Page/Page column 21
(2010/04/23)
-
- Orally active and brain permeable proline amides as highly selective 5HT2c agonists for the treatment of obesity
-
Brain-penetrable proline amides were developed as 5HT2c agonists with more than 1000-fold binding selectivity against 5HT2b receptor. After medicinal chemistry optimization and SAR studies, orally active proline amides with robust efficacy in a rodent foo
- Liu, Kevin K.-C.,Lefker, Bruce A.,Dombroski, Mark A.,Chiang, Phoebe,Cornelius, Peter,Patterson, Terrell A.,Zeng, Yuan,Santucci, Stephanie,Tomlinson, Elizabeth,Gibbons, Colleen P.,Marala, Ravi,Brown, Janice A.,Kong, Jimmy X.,Lee, Eunsun,Werner, Wendy,Wenzel, Zane,Giragossian, Craig,Chen, Hou,Coffey, Steven B.
-
scheme or table
p. 2365 - 2369
(2010/09/03)
-
- Origin of stereocontrol in the construction of the 12-oxatricyclo[6.3.1. 02,7]dodecane ring system by Prins-pinacol reactions
-
(Chemical Equation Presented) Polycyclic products containing the 12-oxatricyclo[6.3.1.02,7]dodecane moiety having either the trans (8a-e) or cis (9a-e) relative configuration of the oxacyclic bridge and the cis angular substituents are formed s
- Overman, Larry E.,Tanis, Paul S.
-
supporting information; experimental part
p. 455 - 463
(2010/03/25)
-
- METHOD OF TREATMENT USING NOVEL ANTAGONISTS OR INVERSE AGONISTS AT OPIOID RECEPTORS
-
A method of treatment using pharmaceutical compositions containing novel antagonists or inverse agonists at opioid receptors for the treatment of binge eating disorder, anorexia nervosa, bulimia nervosa, excess drug or alcohol use, or eating disorder not otherwise specified.
- -
-
-
- Strain release in C-H bond activation?
-
What a relief ! In 1955, strain release was put forward as a reactivity factor to explain the differing reactivity of axial and equitorial alcohols during oxidation. The same rationale may account for the differing rates of activation between axial and equitorial C-H bonds in C-H activation processes (see scheme)
- Chen, Ke,Eschenmoser, Albert,Baran, Phil S.
-
supporting information; experimental part
p. 9705 - 9708
(2010/04/28)
-
- Novel Pyridine Derivatives
-
The invention relates to novel pyridine derivatives, their preparation and their use as pharmaceutically active compounds. Said compounds particularly act as immunosuppressive agents.
- -
-
Page/Page column 10-11
(2009/01/24)
-
- NOVEL HETEROCYCLE COMPOUNDS
-
The present invention relates to novel compounds which are antagonist or inverse agonists at an opioid receptor. Such compounds are useful in the treatment of obesity and related diseases and/or conditions in mammals, particularly humans. Methods of making and using such compounds are also disclosed.
- -
-
Page/Page column 39
(2009/04/24)
-
- DIPHENYL SUBSTITUTED CYCLOALKANES
-
The present invention provides compounds of Formula I which are FLAP inhibitors useful as anti-atherosclerotic, anti-asthmatic, anti-allergic, anti-inflammatory and cytoprotective agents.
- -
-
Page/Page column 39-40
(2009/05/28)
-
- 2-iodoxybenzenesulfonic acid as an extremely active catalyst for the selective oxidation of alcohols to aldehydes, ketones, carboxylic acids, and enones with oxone
-
Electron-donating group-substituted 2-iodoxybenzoic acids (IBXs) such as5-Me-IBX (1g), 5-MeO-IBX (1h), and 4,5-Me2-IBX were superior to IBX 1a as catalysts for the oxidation of alcohols with Oxone (a trad emark of DuPont) under nonaqueous conditions, although Oxone was almost insoluble in most organic solvents. The catalytic oxidation proceeded more rapidly and cleanly in nitromethane. Furthermore, 2-iodoxybenzenesulfonic acid (IBS, 6a) was much more active than modified IBXs. Thus, we established a highly efficient and selective method for the oxidation of primary and secondary alcohols to carbonyl compounds such as aldehydes, carboxylic acids, and ketones with Oxone in nonaqueous nitromethane, acetonitrile, or ethyl acetate in the presence of 0.05-5molpercentof 6a, which was generated in situ from 2-iodobenzenesulfonic acid (7a) or its sodium salt. Cycloalkanones could be further oxidized to α,β- cycloalkenones or lactones by controlling the amounts of Oxone under the same conditions as above. When Oxone was used under nonaqueous conditions, Oxone wastes could be removed by simple filtration. Based on theoretical calculations, we considered that the relatively ionic character of the intramolecular hypervalent iodine-OSO2 bond of IBS might lower the twisting barrier of the alkoxyperiodinane intermediate 16.
- Uyanik, Muhammet,Akakura, Matsujiro,Ishihara, Kazuaki
-
supporting information; experimental part
p. 251 - 262
(2009/06/28)
-
- MELANOCORTIN RECEPTOR AGONISTS
-
The present invention relates to a compound of the following formula 1, pharmaceutically acceptable salt and isomer thereof effective as agonist of melanocortin receptor, and an agonistic composition of melanocortin receptor comprising the same as active ingredient.
- -
-
Page/Page column 27
(2008/06/13)
-
- Substituted 2-oxo-azepane derivatives are potent, orally active γ-secretase inhibitors
-
A hydroxamic acid screening hit 1 was elaborated to 5,5-dimethyl-2-oxoazepane derivatives exhibiting low nanomolar inhibition of γ-secretase, a key proteolytic enzyme involved in Alzheimer's disease. Early ADME data showed a high metabolic clearance for t
- Kitas, Eric A.,Galley, Guido,Jakob-Roetne, Roland,Flohr, Alexander,Wostl, Wolfgang,Mauser, Harald,Alker, Andre M.,Czech, Christian,Ozmen, Laurence,David-Pierson, Pascale,Reinhardt, Dieter,Jacobsen, Helmut
-
p. 304 - 308
(2008/04/07)
-
- Cyclization of N,N-diethylgeranylamine N-oxide in one-pot operation: preparation of cyclic terpenoid-aroma chemicals
-
Acid promoted cyclization of the geranylamine N-oxide (E)-4 followed by base-catalyzed intramolecular aldol condensation afforded 1-acetyl-4,4-dimethyl-1-cyclohexene (7) in one-pot operation. Reduction of 7, which possess strong fruity odor, followed by lipase-catalyzed kinetic resolution furnished the acetate (R)-26 (>49.9% yield, >99% ee) and the recovered alcohol (S)-25 (>49.9% yield, >99% ee, herbal odor).
- Takabe, Kunihiko,Yamada, Takashi,Miyamoto, Takenori,Mase, Nobuyuki
-
scheme or table
p. 6016 - 6018
(2009/04/11)
-
- Hydrogenated Benzo (C) Thiophene Derivatives as Immunomodulators
-
The invention relates to novel thiophene derivatives, their preparation and their use as pharmaceutically active compounds. Said compounds particularly act as immunosuppressive agents.
- -
-
Page/Page column 20
(2008/12/07)
-
- Tricyclic compounds, a process for their preparation and pharmaceutical compositions containing them
-
Compounds of formula (I): wherein A represents a 5, 6 or 7-membered (hetero)aromatic or non-aromatic ring,n and n′ represent 0, 1 or 2X represents an alkylene chain as defined in the description,R3 represents an aryl or heteroaryl group,one of the groups R1 and R2 represents a hydrogen atom and the other represents a group of formula (II) as defined in the description. Medicinal products containing the same which are useful in treating conditions involving a defect in apoptosis.
- -
-
Page/Page column 12
(2008/12/07)
-
- Reduction of α,β-unsaturated ketones with diphenylsilanes bearing several substituents on their phenyl moiety catalyzed by rhodium-phosphine complexes
-
1,4-Addition product was afforded exclusively by rhodiumphosphine complex-catalyzed hydrosilylation by using 2-cyclohexen-1-one and a dihydrosilane bearing an ether substituent in spite of the fact that dihydrosilanes were believed to give 1,2-addition product selectively. Copyright
- Imao, Daisuke,Hayama, Miyuki,Ishikawa, Kohta,Ohta, Tetsuo,Ito, Yoshihiko
-
p. 366 - 367
(2007/10/03)
-
- Dibenzyl Amine Compounds and Derivatives
-
Dibenzyl amine compounds and derivatives, pharmaceutical compositions containing such compounds and the use of such compounds to elevate certain plasma lipid levels, including high density lipoprotein-cholesterol and to lower certain other plasma lipid levels, such as LDL-cholesterol and triglycerides and accordingly to treat diseases which are exacerbated by low levels of HDL cholesterol and/or high levels of LDL-cholesterol and triglycerides, such as atherosclerosis and cardiovascular diseases in some mammals, including humans.
- -
-
Page/Page column 94
(2010/11/28)
-
- NOVEL THIOPHENE DERIVATIVES
-
The invention relates to novel thiophene derivatives, their preparation and their use as pharmaceutically active compounds. Said compounds particularly act as immunosuppressive agents.
- -
-
Page/Page column 25-26
(2008/06/13)
-
- HCV INHIBITING BI-CYCLIC PYRIMIDINES
-
The present invention relates to the use of bi-cyclic pyrimidines as inhibitors of HCV replication as well as their use in pharmaceutical compositions aimed to treat or combat HCV infections. In addition, the present invention relates to processes for pre
- -
-
Page/Page column 53; 54
(2010/10/20)
-
- Nucleophilic substitution reactions of sulfur-substituted cyclohexanone acetals: An analysis of the factors controlling stereoselectivity
-
The reactions of cyclohexanone acetals substituted with thiophenyl groups (and other heteroatoms) at C-2 demonstrate the powerful influence that these substituents have on the stereoselectivity of nucleophilic substitution reactions. The trans selectivities of these reactions correlate with the behavior of the corresponding ketones. These experiments lend support to the possibility that the reactions of the acetals, which proceed via oxocarbenium ions, are operating under Felkin-Anh control.
- Billings, Susan B.,Woerpel
-
p. 5171 - 5178
(2007/10/03)
-
- COMPOUNDS FOR INHIBITING KSP KINESIN ACTIVITY
-
The present invention provides compounds of Formula (I) (wherein R1, R3, X, W, Z and ring Y are as defined herein). The present invention also provides compositions comprising these compounds that are useful for treating cellular proliferative diseases or disorders associated with KSP kinesin activity and for inhibiting KSP kinesin activity.
- -
-
Page/Page column 101
(2010/11/23)
-
- D-xylopyranosyl-phenyl-substituted cycles, medicaments containing such compounds, their use and process for their manufacture
-
D-Glucopyranosyl-phenyl-substituted cycles of general formula I wherein the groups R1 to R6, Z, Cy and R7a, R7b, R7c, R7d are defined as in claim 1, have an inhibiting effect on the sodium-dependent glucose cotransporter SGLT. The present invention also relates to pharmaceutical compositions for the treatment of metabolic disorders.
- -
-
Page/Page column 21
(2010/02/15)
-
- RuHCl(CO)(PPh3)3-catalyzed chemoselective transfer-hydrogenation of enones leading to saturated ketones
-
The highly chemoselective transfer-hydrogenation of α,β- unsaturated ketones to give saturated ketones was achieved using RuHCl(CO)(PPh3)3 as a catalyst. In addition to α,β-unsaturated ketones, other enones, containing a remote C=C bond, were also reduced to give saturated ketones in good to excellent yields with high selectivity. Georg Thieme Verlag Stuttgart.
- Doi, Takashi,Fukuyama, Takahide,Horiguchi, Jiro,Okamura, Takahiro,Ryu, Ilhyong
-
p. 721 - 724
(2007/10/03)
-
- HYDROGENATED BENZO (C) THIOPHENE DERIVATIVES AS IMMUNOMODULATORS
-
The invention relates to novel thiophene derivatives, their preparation and their use as pharmaceutically active compounds. Said compounds particularly act as immunosuppressive agents.
- -
-
Page/Page column 54
(2010/11/24)
-
- Direct conversion of N-methoxy-N-methylamides (Weinreb amides) to ketones via a nonclassical Wittig reaction
-
(Chemical Equation Presented) N-Methoxy-N-methylamides (Weinreb amides) are converted efficiently into ketones by reaction with alkylidenetriphenylphosphoranes and in situ hydrolysis of the product.
- Murphy, John A.,Commeureuc, Aurelien G. J.,Snaddon, Thomas N.,McGuire, Thomas M.,Khan, Tanweer A.,Hisler, Kevin,Dewis, Mark L.,Carling, Robert
-
p. 1427 - 1429
(2007/10/03)
-
- CHEMICAL COMPOUNDS
-
The present invention relates to novel compounds with a variety of therapeutic uses, more particularly novel substituted cyclic alkylidene compounds that are particularly useful for selective estrogen receptor modulation.
- -
-
Page/Page column 51-52
(2008/06/13)
-
- Porphyrins with exocyclic rings. Part 21: Influence of pyrrolic and carbocyclic ring alkyl substituents on the synthesis of porphyrins bearing six-membered exocyclic rings
-
A series of 5-substituted 4,5,6,7-tetrahydroindoles were prepared by reacting 4-substituted cyclohexanones with phenylhydrazones derived from esters of acetoacetic acid under Knorr-type reaction conditions. Related 6,6-dimethyltetrahydroindoles were also
- Shiner, Craig M.,Lash, Timothy D.
-
p. 11628 - 11640
(2007/10/03)
-