- REACTION OF SELENIUM DIOXIDE WITH 3-HYDROXY-1,6-DIOLEFINS. Formation of 8-oxa-3-selenabicyclo1,5>octanes and other selenoorgano compounds
-
The formation of selenium containing products during the reaction of selenium dioxide with hydroxydiolefins has been confirmed through the synthesis and reactivity studies with selected model compounds.The isolation of 8-oxa-3-selenabicyclo1,5>octanes and dimeric selenium compounds has been observed with cyclohexanic and cyclopentanic derivatives.
- Medarde, Manuel,Lopez, Jose Luis,Morillo, M Angeles,Tome, Fernando,Adeva, Marta,Feliciano, Arturo San
-
-
Read Online
- ODORANT COMPOUND
-
The present invention relates to the field of perfumery. More particularly, it concerns a compound of formula (I) as defined herein below, and its uses as perfuming ingredients. Therefore, following what is mentioned herein, the present invention comprises the invention compound as part of a perfuming composition or of a perfumed consumer product. Moreover, the present invention relates to a properfume compound suitable to release the compound of formula (I).
- -
-
Page/Page column 15; 17
(2021/10/22)
-
- PROCESS FOR PREPARING PERFUMING INTERMEDIATE
-
The present invention relates to the field of organic synthesis and more specifically it concerns a process for preparing compound of formula (I) by a cross metathesis reaction. Said compound of formula (I) is valuable new chemical intermediate for producing perfuming ingredients and is also part of the present invention.
- -
-
Page/Page column 40-41
(2021/09/11)
-
- Discovery of N-Substituted 3-Amino-4-(3-boronopropyl)pyrrolidine-3-carboxylic Acids as Highly Potent Third-Generation Inhibitors of Human Arginase i and II
-
Recent efforts to identify new highly potent arginase inhibitors have resulted in the discovery of a novel family of (3R,4S)-3-amino-4-(3-boronopropyl)pyrrolidine-3-carboxylic acid analogues with up to a 1000-fold increase in potency relative to the current standards, 2-amino-6-boronohexanoic acid (ABH) and N-hydroxy-nor-l-arginine (nor-NOHA). The lead candidate, with an N-2-amino-3-phenylpropyl substituent (NED-3238), example 43, inhibits arginase I and II with IC50 values of 1.3 and 8.1 nM, respectively. Herein, we report the design, synthesis, and structure-activity relationships for this novel series of inhibitors, along with X-ray crystallographic data for selected examples bound to human arginase II.
- Van Zandt, Michael C.,Jagdmann, G. Erik,Whitehouse, Darren L.,Ji, Minkoo,Savoy, Jennifer,Potapova, Olga,Cousido-Siah, Alexandra,Mitschler, Andre,Howard, Eduardo I.,Pyle, Anna Marie,Podjarny, Alberto D.
-
p. 8164 - 8177
(2019/10/02)
-
- Reactivity of Lithium β-Ketocarboxylates: The Role of Lithium Salts
-
Lithium β-ketocarboxylates 1(COOLi), prepared by the reaction of lithium enolates 2(Li+) with carbon dioxide, readily undergo decarboxylative disproportionation in THF solution unless in the presence of lithium salts, in which case they are indefinitely stable at room temperature in inert atmosphere. The availability of stable THF solutions of lithium β-ketocarboxylates 1(COOLi) in the absence of carbon dioxide allowed reactions to take place with nitrogen bases and alkyl halides 3 to give α-alkyl ketones 1(R) after acidic hydrolysis. The sequence thus represents the use of carbon dioxide as a removable directing group for the selective monoalkylation of lithium enolates 2(Li+). The roles of lithium salts in preventing the disproportionation of lithium β-ketocarboxylates 1(COOLi) and in determining the course of the reaction with bases and alkyl halides 3 are discussed.
- Berton, Mateo,Mello, Rossella,Williard, Paul G.,González-Nú?ez, María Elena
-
supporting information
p. 17414 - 17420
(2017/12/15)
-
- Cobalt Catalysis for Enantioselective Cyclobutanone Construction
-
Over the past 40 years, intramolecular hydroacylation has favored five-membered rings, in preference to four membered rings. Herein, we report a catalyst derived from earth-abundant cobalt that enables preparation of cyclobutanones, with excellent regio-,
- Kim, Daniel K.,Riedel, Jan,Kim, Raphael S.,Dong, Vy M.
-
supporting information
p. 10208 - 10211
(2017/08/10)
-
- Developing the Saegusa-Ito Cyclisation for the Synthesis of Difluorinated Cyclohexenones
-
Palladium(II)-catalysed cycloalkenylation (Saegusa-Ito cyclisation) has been used for the first time to transform difluorinated silylenol ethers to difluorinated cycloalkenones under mild conditions. The silylenol ether precursors were prepared in two high-yielding steps from trifluoroethanol, and cyclised in moderate to good yields. A combination of air and copper(I) chloride in acetonitrile gave the turnover of the initial palladium(II) salt, whereas the provision of an oxygen atmosphere ensured more rapid reaction. Annulations required a minimum level of substitution on the chain, but failed when the alkene was substituted. Annelations allowed a range of n,6-bicyclic systems to be prepared and afforded three products, in which heterocycles were fused to the new cyclohexenone. The least substituted system explored underwent cyclisation followed by terminal oxidation to a cyclic enal, which corresponded to a Wacker product of unusual regiochemistry.
- Percy, Jonathan M.,McCarter, Adam W.,Sewell, Alan L.,Sloan, Nikki,Kennedy, Alan R.,Hirst, David J.
-
supporting information
p. 19119 - 19127
(2016/01/26)
-
- Hydrogen-bond-activated palladium-catalyzed allylic alkylation via allylic alkyl ethers: Challenging leaving groups
-
C-O bond cleavage of allylic alkyl ether was realized in a Pd-catalyzed hydrogen-bond-activated allylic alkylation using only alcohol solvents. This procedure does not require any additives and proceeds with high regioselectivity. The applicability of this transformation to a variety of functionalized allylic ether substrates was also investigated. Furthermore, this methodology can be easily extended to the asymmetric synthesis of enantiopure products (99% ee).
- Huo, Xiaohong,Quan, Mao,Yang, Guoqiang,Zhao, Xiaohu,Liu, Delong,Liu, Yangang,Zhang, Wanbin
-
supporting information
p. 1570 - 1573
(2014/04/17)
-
- One-pot sequential 1,4- and 1,2-reductions of α,β-unsaturated δ-lactones to the corresponding δ-lactols with CuCl and NaBH 4 in methanol
-
An efficient, one-pot method for the highly chemoselective synthesis of δ-lactols from α,β-unsaturated δ-lactones using CuCl and NaBH4 in methanol was developed. Georg Thieme Verlag Stuttgart. New York.
- Matsumoto, Yasunobu,Yonaga, Masahiro
-
p. 1764 - 1768
(2014/08/05)
-
- RING CONSTRAINED ANALOGS AS ARGINASE INHIBITORS
-
The inventive boronic acid analogs are potent inhibitors of Arginase I and II activity. These compounds are candidate therapeutics for treating a disease or disorder associated with an imbalance in the activity or concentration of cellular arginase I and
- -
-
Paragraph 0050
(2013/11/05)
-
- Versatile access to chiral indolines by catalytic asymmetric fischer indolization
-
"Fisching" for complexity: The chiral Bronsted acid (R)-STRIP catalyzes the asymmetric Fischer indolization of a range of monosubstituted cyclopentanones and cyclohexanones to give chiral fused indolines bearing a quaternary stereogenic center at the 3-position. The method has been extended to include substrates bearing a tethered nucleophile, thus allowing for enantioselective indolization/ring-closing cascades to complex propellanes featuring two vicinal quaternary stereocenters. Copyright
- Martinez, Alberto,Webber, Matthew J.,Mueller, Steffen,List, Benjamin
-
p. 9486 - 9490
(2013/09/23)
-
- BORONATES AS ARGINASE INHIBITORS
-
Compounds according to Formula I are potent inhibitors of Arginase I and II activity: (I) where R1, R2, R3, R4, D, W, X, Y, and Z are defined in the specification. The invention also provides pharmaceutical compositions of the compounds and methods of their use in treating or preventing a disease or a condition associated with arginase activity.
- -
-
Page/Page column 37-38
(2012/05/19)
-
- Reductive cyclization cascades of lactones using SmI2-H 2O
-
Lactones bearing two alkenes or an alkene and an alkyne undergo reductive cyclization cascades upon treatment with SmI2-H2O, giving decorated azulene motifs in excellent yields with good diastereocontrol.
- Parmar, Dixit,Price, Kieran,Spain, Malcolm,Matsubara, Hiroshi,Bradley, Paul A.,Procter, David J.
-
supporting information; experimental part
p. 2418 - 2420
(2011/04/25)
-
- C-N bond cleavage of allylic amines via hydrogen bond activation with alcohol solvents in Pd-catalyzed allylic alkylation of carbonyl compounds
-
Hydrogen-bond-activated C-N bond cleavage of allylic amines was realized in Pd-catalyzed allylic alkylation to form the C-C bond product. The method could be expanded to a series of allylic amines and carbonyl compounds with excellent results. It provides a new and convenient access to C-C bond formation based on Pd-catalyzed allylic alkylation of allylic amines by using only inexpensive alcohol solvents.
- Zhao, Xiaohu,Liu, Delong,Guo, Hui,Liu, Yangang,Zhang, Wanbin
-
supporting information; experimental part
p. 19354 - 19357
(2012/01/06)
-
- A flexible, unified radical-based approach to polycyclic structures
-
Cis- and trans-decalins, trans-perhydroazulenes, and [5.3.1]-bicyclo- undecanone scaffolds can be readily constructed starting from unsaturated ketones and using the degenerative xanthate transfer technology to accomplish unusual and otherwise difficult r
- Heng, Rama,Zard, Samir Z.
-
experimental part
p. 3396 - 3404
(2011/06/25)
-
- Generation and trapping of cyclopentenylidene gold species: Four pathways to polycyclic compounds
-
Cyclopentenylidene gold complexes can easily be formed from vinyl allenes through a Nazarov-like mechanism. Such carbenes may transform in four different ways into polycyclic frameworks: electrophilic cyclopropanation, C-H insertion, C-C migration, or proton shift. We have studied the selectivity of these different pathways and used our findings for the expedient preparation of valuable complex molecules. An application to the total synthesis of a natural product, Δ9(12)-capnellene,is presented. DFT computations were carried out to shed light on the me chanisms.
- Lemiere, Gilles,Gandon, Vincent,Cariou, Kevin,Hours, Alexandra,Fukuyama, Takahide,et al.
-
scheme or table
p. 2993 - 3006
(2009/09/04)
-
- Gold- Vs. platinum-catalyzed polycyclizations by O-acyl migration. solvent-free reactions
-
Polycyclic derivatives incorporating a cyclopropyl group have been efficiently synthesized from propargyl acetates using platinum(II), gold(I) and gold(III) catalysis. These reactions which are also viable for the preparation of medium-sized rings, proceed with a complete diastereocontrol and can also be run in neat conditions.
- Moreau, Xavier,Goddard, Jean-Philippe,Bernard, Matthieu,Lemiere, Gilles,Lopez-Romero, Juan Manuel,Mainetti, Emily,Marion, Nicolas,Mouries, Virginie,Thorimbert, Serge,Fensterbank, Louis,Malacria, Max
-
scheme or table
p. 43 - 48
(2009/04/08)
-
- A concise synthetic pathway towards 5-substituted indolizidines
-
The total synthesis of 5-(2′-hydroxyethyl)indolizidine via 5-thioindolizidinone is described. The key step is the transformation of 5-thioindolizidinone via Eschenmoser's sulfide contraction. The racemic mixture of 5R,9R- and 5S,9S-5-(2′-hydroxyethyl)indolizidine was obtained in seven steps in 17% overall yield from 2-allyl cyclopentanone.
- Varga, Tamás R.,Nemes, Péter,Mucsi, Zoltán,Scheiber, Pál
-
p. 1159 - 1161
(2007/10/03)
-
- Baeyer-Villiger oxidations catalyzed by engineered microorganisms: Enantioselective synthesis of δ-valerolactones with functionalized chains
-
Cyclohexanone monooxygenase (CHMO) from Acinetobacter sp NCIMB 9871 expressed in baker's yeast and in E. coli and cyclopentanone monooxygenase (CPMO) from Comamonas (previously Pseudomonas) sp. NCIMB 9872 expressed in E. coli are new bioreagents for Baeye
- Wang, Shaozhao,Chen, Gang,Kayser, Margaret M.,Iwaki, Hiroaki,Lau, Peter C.K.,Hasegawa, Yoshie
-
p. 613 - 621
(2007/10/03)
-
- Heterobicyclic and tricyclic nitric oxide synthase inhibitors
-
The current invention discloses useful bicyclic and tricyclic amidino derivative compounds, pharmaceutical compositions containing these novel compounds, and to their use as nitric oxide synthase inhibitors.
- -
-
-
- Synthesis of enantiomerically pure bicyclic lactams
-
Enantiomerically pure homologous 1-azabicyclo-[x.y.0]alkanones (x = 4-5, y = 4-7) can be synthesized by ring closing olefin metathesis using Grubbs' ruthenium catalyst. By starting from monocyclic lactams, the bicyclic products, even eight- and nine-membered rings, are formed in high yields. The monocyclic lactames can be obtained enantiomerically pure by enzyme-catalyzed kinetic resolution.
- Diedrichs, Nicole,Westermann, Bernhard
-
p. 1127 - 1129
(2007/10/03)
-
- SYNTHESIS OF 3',4'-α-PROPYLENE-2',3'-DIDEOXYNUCLEOSIDES
-
In order to obtain a high degree of rigidity within the sugar moiety of nucleosides, some bicyclic pyrimidine nucleoside analogues were synthesized starting from cyclopentanone.The C-4'-substituent is fused to the C-3'-position via a propylene to give a
- Bjoersne, Magnus,Szabo, Tomas,Samuelsson, Bertil,Classon, Bjoern
-
p. 279 - 282
(2007/10/02)
-
- Versatile Desilylative Cross-Coupling of Silyl Enol Ethers and Allylic Silanes via Oxovanadium-Induced Chemoselective One-Electron Oxidation
-
The chemoselective cross-coupling of silyl enol ethers and allylic silanes to γ,δ-unsaturated ketones is achieved by the oxovanadium(V)-induced oxidative desilylation of the more readily oxidizable organosilicon compounds.
- Hirao, Toshikazu,Fujii, Takashi,Ohshiro, Yoshiki
-
p. 10207 - 10214
(2007/10/02)
-
- Origin of the Regiochemistry in the Photochemical Cycloaddition Reaction of 2-Cyclopentenone with Allene: Trapping of Triplet 1,4-Biradical Intermediates with Hydrogen Selenide
-
The photochemical cycloaddition reaction between 2-cyclopentenone and allene in toluene at -78 deg C yields cyclobutane adducts with head-to-head and head-to-tail regiochemistry in a ratio of 88:12.In the presence of high concentrations of hydrogen seleni
- Maradyn, David J.,Sydnes, Leiv K.,Weedon, Alan C.
-
p. 2413 - 2416
(2007/10/02)
-
- NiCl2(PPh3)2-Zn Promoted Deallyloxycarbonylative Directed Aldol Reaction of Allyl β-Keto Carboxylates with Aldehydes th β-Hydroxy Ketones
-
Regio- and chemospecific deallyloxycarbonylative aldol reaction of allyl (or -lic) α,α-disubstituted β-keto carboxylate with aldehyde was effectively promoted by Ni(0) (NiCl2(PPh3)2-Zn), in which the allyloxycarbonyl group (-COOCH2CH=CH2) was replaced to 1-hydroxyalkyl group (-CH(OH)R, R=alkyl, vinyl, aryl) under mild reaction conditions.
- Nokami, Junzo,Konishi, Haruhisa,Matsuura, Hiroyuki
-
p. 2023 - 2026
(2007/10/02)
-
- Regioselective Aza-Cope Rearrangement of α-Halogenated and Nonhalogenated Imines
-
The 3-aza-Cope rearrangement of α-halogenated and nonhalogenated ketimines by deprotonation of the corresponding iminium salts was found to be an especially facile and regioselective process.Deuterium labeling studies supported the proposed mechanism which required the rearrangement to be highly concerted.
- Welch, John T.,Corte, Bart De,Kimpe, Norbert De
-
p. 4981 - 4983
(2007/10/02)
-
- Catalytic Allylation of 1-Trimethylsilyloxycyclopent-1-ene into 2-Allylcyclopentanone over Palladium supported on Silica
-
1-Trimethylsilyloxycyclopent-1-ene can be catalytically converted into 2-allylcyclopentanone by its reaction with diallyl carbonate over palladium supported on silica.
- Baba, T.,Nakano, K.,Nishiyama, S.,Tsurya, S.,Masai, M.
-
p. 348 - 349
(2007/10/02)
-
- A New Route to the Prostaglandin Skeleton via Radical Alkylation. Synthesis of 6-Oxoprostaglandin E1
-
A new, mild, and efficient method for the construction of the prostanoid skeleton involving cuprate addition to α-(phenylseleno)cyclopentenones followed by radical-based coupling to the resulting products with allylstannane derivatives is described.The method is applied to the synthesis of 6-oxoprostaglandin E1, a biologically active and naturally occurring compound.
- Toru, Takeshi,Yamada, Yoshio,Ueno, Toshio,Maekawa, Eturo,Ueno, Yoshio
-
p. 4815 - 4817
(2007/10/02)
-
- Intramolecular cycloadditions of vinylketenes to olefins. Part II. The synthesis of a linear annelated triquinane derivative.
-
Regioselective formation of vinylketene 3, followed by its stereoselective intramolecular cycloaddition with an olefin, yielded the linear annelated cis-anti-cis triquinane precursor 1.
- Mesmaeker, Alain De,Veenstra, Siem J.,Ernst, Beat
-
p. 459 - 462
(2007/10/02)
-
- New Methods for the Syntheses of α,β-Unsaturated Ketones, Aldehydes, and Nitriles by the Palladium-Catalyzed Reactions of Allyl β-Oxo Esters, Allyl 1-Alkenyl Carbonates, and Allyl α-Cyano Esters
-
Allyl β-oxo esters, allyl 1-alkenyl carbonates, and allyl α-cyano esters are converted into α,β-unsaturated ketones, aldehydes, and nitriles by palladium-catalyzed intramolecular decarboxylation-dehydrogenation.Palladium-phosphine complexes such as Pd(OAc)2-PPh3, Pd(OAc)2-dppe, or Pd2(dba)3*CHCl3-PPh3, are effective catalysts.Yields depend on solvents and on the mole ratio of palladium to phosphine.The optimum Pd/P ratio for each substrate was determined.Use of nitriles as solvents is essential for the dehydrogenation.
- Minami, Ichiro,Nisar, Mohammad,Yuhara, Masami,Shimizu, Isao,Tsuji, Jiro
-
p. 992 - 998
(2007/10/02)
-
- ENONE FORMATION FROM ALLYL β-KETO ESTERS ALKENYL ELLYL CARBONATES, SILYL ENOL ETHERS, AND ENOL ACETATES BY THE PHOSPHINE-FREE PALLADIUM CATALYST
-
The effect of phosphine ligands on the palladium catalyzed enone formation from allyl β-keto esters, alkenyl allyl carbonates, silyl enol ethers, and enol acetates has been reinvestigated, and clean enone formation was observed by a phosphine-free palladium catalyst.
- Tsuji, Jiro,Minami, Ichiro,Shimizu, Isao,Kataoka, Hideaki
-
p. 1133 - 1136
(2007/10/02)
-
- ALLYLATION OF KETONES VIA THEIR ENOL ACETATES CATALYZED BY PALLADIUM-PHOSPHINE COMPLEXES AND ORGANOTIN COMPOUNDS
-
Enol acetates are converted to allyl ketones by the reaction of allylic carbonates in the presence of palladium-phosphine complex and tin alkoxide as bimetallic catalysts.
- Tsuji, Jiro,Minami, Ichiro,Shimizu, Isao
-
p. 4713 - 4714
(2007/10/02)
-
- PALLADIUM-CATALYZED ALLYLATION OF KETONES AND ALDEHYDES VIA ALLYL ENOL CARBONATES
-
Rearrangement of allyl enol carbonates, prepared from ketones or aldehydes by trapping their enolates with allyl chloroformate, to give α-allyl ketones or aldehydes regioselectively is catalyzed by palladium-phosphine complexes under mild conditions.
- Tsuji, Jiro,Minami, Ichiro,Shimizu, Isao
-
p. 1793 - 1796
(2007/10/02)
-
- PALLADIUM-CATALYZED SYNTHESIS OF α,β-UNSATURATED KETONES FROM KETONES VIA ALLYL ENOL CARBONATES
-
Allyl enol carbonates, prepared by quenching ketone enolates with allyl chloroformate, are converted to α,β-unsaturated ketones with Pd(OAc)2-dppe catalyst in CH3CN.
- Shimizu, Isao,Minami, Ichiro,Tsuji, Jiro
-
p. 1797 - 1800
(2007/10/02)
-
- Tris(dialkylamino)sulfonium Enolates. Synthesis, Structure, and Reactions
-
A mixture of an enol trimethylsilyl ether and a fluoride salt exists in a dynamic equilibrium with an enolate species and fluorotrimethylsilane.Evacuation of an equimolar mixture of an enol trimethylsilyl ether of benzyl methyl ketone and tris(diethylamino)sulfonium (TAS) difluorotrimethylsiliconate produces fluorotrimethylsilane as the volatile fraction and the corresponding TAS enolate as air-sensitive crystals.The conductivity measurement and the 1H and 13C NMR analysis have substantiated the ionic nature of the TAS enolate in THF.The NMR chemical shifts are interpreted in terms of the electron distribution.The isolated TAS enolate undergoes O-acetylation with acetic anhydride and C-alkylation with methyl iodide exclusively.TAS enolate intermediates generated in situ from a series of enol silyl ethers and TAS difluorotrimethylsiliconate react with various active organic halides under mild conditions to give the regiospecific C-alkylation products.The in situ formed enolates react with aldehyde substrates to afford the β-trimethylsiloxy ketone adducts.In most cases, the reaction is kinetically controlled and the major products have erythro stereochemistry regardless of enolate configuration.This aldol reaction is postulated to proceed via an acyclic, extended transition state, in contrast to ordinary aldol reactions of Lewis acid coordinated enolates, which take place by way of six-membered chelate transition states.
- Noyori, R.,Nishida, I.,Sakata, J.
-
p. 1598 - 1608
(2007/10/02)
-
- PALLADIUM-CATALYZED ALLYLATION OF KETONES AND ALDEHYDES WITH ALLYLIC CARBONATES VIA SILYL ENOL ETHERS UNDER NEUTRAL CONDITIONS
-
Silyl enol ethers are converted to 2-allyl ketones and aldehydes by the reaction with allylic carbonates in the presence of a palladium-phosphine catalyst.
- Tsuji, Jiro,Minami, Ichiro,Shimizu, Isao
-
p. 1325 - 1326
(2007/10/02)
-
- Alkylation via tris(dialkylamino)sulfonium enolates
-
Tris(dialkylamino)sulfonium enolates generated from tris(diethylamino)sulfonium difluorotrimethylsiliconate and enol silyl ethers are readily alkylated by various alkyl halides under mild conditions.
- Noyori,Nishida,Sakata
-
p. 2085 - 2088
(2007/10/02)
-