- Formal Total Syntheses of (+)- and (–)-ar-Macrocarpene via Rh(I)-BINAP Catalyzed Conjugate Addition
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Catalytic asymmetric formal total syntheses of both antipodes of sesquiterpene, (+)-ar-macrocarpene (1) and (–)-ar-macrocarpene (ent-1) has been achieved from 5,5-dimethyl-(3-p-tolyl)cyclohexanone 12. Enantioenriched compound 12 was obtained in excellent
- Khatua, Arindam,Pal, Souvik,Bisai, Vishnumaya
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Read Online
- Concise total syntheses of (+)- and (?)-ar-macrocarpene
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Concise catalytic asymmetric total syntheses of both the enantiomers of aromatic sesquiterpenes, (+)-ar-macrocarpene (1) and (–)-ar-macrocarpene (ent-1) is featured in 4 steps, 66.0% overall yields from commercially available 5,5-dimethylcyclohexane 1,3-d
- Khatua, Arindam,Shaw, Kundan,Bisai, Vishnumaya
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- PIKFYVE KINASE INHIBITORS
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The present invention relates to compounds useful as inhibitors of phosphatidylinositol-3-phosphate 5-kinase (PIKfyve) as well as their use for treating diseases and disorders associated with PIKfyve.
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Page/Page column 363; 364
(2021/08/20)
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- Platinum-Catalyzed α,β-Desaturation of Cyclic Ketones through Direct Metal–Enolate Formation
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The development of a platinum-catalyzed desaturation of cyclic ketones to their conjugated α,β-unsaturated counterparts is reported in this full article. A unique diene-platinum complex was identified to be an efficient catalyst, which enables direct metal-enolate formation. The reaction operates under mild conditions without using strong bases or acids. Good to excellent yields can be achieved for diverse and complex scaffolds. A wide range of functional groups, including those sensitive to acids, bases/nucleophiles, or palladium species, are tolerated, which represents a distinct feature from other known desaturation methods. Mechanistically, this platinum catalysis exhibits a fast and reversible α-deprotonation followed by a rate-determining β-hydrogen elimination process, which is different from the prior Pd-catalyzed desaturation method. Promising preliminary enantioselective desaturation using a chiral-diene-platinum complex has also been obtained.
- Chen, Ming,Dong, Guangbin
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supporting information
p. 7956 - 7961
(2021/03/01)
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- Visible Light-Mediated Photochemical Reactions of 2-(2′-Alkenyloxy)cycloalk-2-enones
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The title compounds were prepared, and their reactivity was studied upon sensitized irradiation at λ = 420 nm. Thioxanthen-9-one was employed as the sensitizer at a loading of 10 mol % in small-scale reactions and of 2.5 mol % on a larger scale. Cyclohex-
- Gra?l, Raphaela,Jandl, Christian,Bach, Thorsten
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p. 11426 - 11439
(2020/10/12)
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- Enantioselective Synthesis of cis-Decalin Derivatives by the Inverse-Electron-Demand Diels–Alder Reaction of 2-Pyrones
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A novel strategy for the synthesis of cis-decalins by an ytterbium-catalyzed asymmetric inverse-electron-demand Diels–Alder reaction of 2-pyrones and silyl cyclohexadienol ethers is reported here. A broad range of synthetically important cis-decalin derivatives with multiple contiguous stereogenic centers and functionalities are obtained in good yields and stereoselectivities. A full set of diastereomeric substituted cis-decalin motifs are readily accessible by tuning the absolute configurations of substituted silyl cyclohexadienol ethers (R or S) as well as the ligands (R or S). The synthetic potential is showcased by the enantioselective total synthesis of 4-amorphen-11-ol, and further demonstrated by the first total synthesis of cis-crotonin.
- Cai, Quan,Li, Zhan-Ting,Si, Xu-Ge,Zhang, Zhi-Mao,Zheng, Cheng-Gong
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supporting information
p. 18412 - 18417
(2020/08/21)
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- Graphene-induced hierarchical mesoporous MgO for the Claisen-Schmidt condensation reaction
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Hierarchical mesoporous MgO (HMM) is synthesized in the presence of graphene by a simple hydrothermal homogeneous precipitation route using urea as the precipitating reagent. Characterization of the HMM particles by means of spectroscopy and microscopy techniques, among others, indicates that HMM exposes the (111) crystal faces and possesses a specific surface area of 138 m2 g-1 and a pore size of about 0.33 m2 g-1. HMM exhibits higher activity for the Claisen-Schmidt condensation reaction than a conventionally prepared MgO catalyst, with a maximum turn over frequency of 1.34 × 10-4 s-1. Since the deactivation of the catalyst is mainly due to the formation of polyaromatic ketones in the reaction process, the catalyst can be readily regenerated through calcination.
- Qi, Xiaoxia,Yan, Xirui,Peng, Wencai,Zhang, Jianshu,Tong, Yanbin,Li, Jun,Sun, Dekui,Hui, Ge,Zhang, Jinli
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p. 4698 - 4705
(2019/03/26)
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- Enantioselective Intermolecular [2+2] Photocycloaddition Reaction of Cyclic Enones and Its Application in a Synthesis of (-)-Grandisol
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The intermolecular [2+2] photocycloaddition of typical cyclic α,β-unsaturated enones, such as 2-cyclohexenone, with olefins was performed in moderate to good yields (42-82%) and with high enantioselectivity (82%-96% ee). An unusual substitution pattern at the chiral oxazaborolidine-AlBr3 Lewis acid complex that promotes the reaction was found to be crucial for the success of the reaction. The method was applied to the enantioselective synthesis of the monoterpene (-)-grandisol, which could be accomplished in six steps and with an overall yield of 13% starting from 3-methyl-2-cyclohexenone.
- Poplata, Saner,Bach, Thorsten
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supporting information
p. 3228 - 3231
(2018/03/13)
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- Acyloxybutadiene tricarbonyl iron complexes as enzyme-triggered CO-releasing molecules (ET-CORMs): A structure-activity relationship study
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A series of η4-acyloxycyclohexadiene-Fe(CO)3 complexes was prepared and fully characterized by spectroscopic methods including single crystal X-ray diffraction. For this purpose a new synthetic access to differently acylated 1,3- and 1,5-dienol-Fe(CO)3 complexes was developed. The enzymatically triggered CO release from these compounds was monitored (detection of CO through GC and/or by means of a myoglobin assay) and the anti-inflammatory effect of the compounds was assessed by a cellular assay based on the inhibition of NO-production by inducible NO synthase (iNOS). It was demonstrated that the properties (rate of esterase-triggered CO release, iNOS inhibition, cytotoxicity) of the complexes strongly depend on the substitution pattern of the π-ligand and the nature of the acyloxy substituent.
- Romanski, Steffen,Kraus, Birgit,Guttentag, Miguel,Schlundt, Waldemar,Rücker, Hannelore,Adler, Andreas,Neud?rfl, J?rg-Martin,Alberto, Roger,Amslinger, Sabine,Schmalz, Hans-Günther
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p. 13862 - 13875
(2013/01/15)
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- Hydroxy-rhodium(I) catalyzed regioselective Michael addition of cyclic enones
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Hydroxy-rhodium catalyzed dimerization of various cyclic enones to the corresponding α-enone adducts is developed. The key feature of this method is that the base-sensitive, highly substituted enones also undergo dimerization and the resultant products ar
- Kumaraswamy, Gullapalli,Rambabu, Dasa
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supporting information; scheme or table
p. 1042 - 1044
(2012/03/26)
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- COMPOUNDS FOR THE TREATMENT AND PREVENTION OF INFLUENZA
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A compound of formula (I) as well as pharmaceutically acceptable salt thereof, wherein R1 to R4 and Ar are as defined in description and in claims, can be used as a medicament.
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- COMPOUNDS FOR THE TREATMENT AND PREVENTION OF INFLUENZA
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A compound of formula (I) as well as pharmaceutically acceptable salt thereof, wherein R1 to R4 and Ar are as defined in description and in claims, can be used as a medicament.
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- COMPOUNDS FOR THE TREATMENT AND PREVENTION OF INFLUENZA
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A compound of formula (I) as well as pharmaceutically acceptable salt thereof, wherein R1 to R4 and Ar are as defined in description and in claims, can be used as a medicament.
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- Dehydrogenation of ketones by pincer-ligated iridium: Formation and reactivity of novel enone complexes
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The transfer dehydrogenation of several ketones by (PCP)IrH2 (PCP = κ3-C6H3-2,6-(CH2P tBu2)2) (1) has been observed. Catalytic turnover was inhibited in most cases by
- Zhang, Xiawei,Wang, David Y.,Emge, Thomas J.,Goldman, Alan S.
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experimental part
p. 253 - 259
(2011/06/17)
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- Enzymatic resolution of racemic secondary cyclic allylic alcohols
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The resolutions of five racemic cyclic alcohols: 6,6-dimethylcyclohex-2-en-1-ol (±)-5, 4,4-dimethylcyclohex-2-en-1-ol (±)-7, 5,5-dimethylcyclohex-2-en-1-ol (±)-11 and isomeric trans-(±)-13 and cis-piperitols (±)-14 are presented. They were resolved by enzymatic esterification with vinyl esters or by enzymatic hydrolysis of their racemic esters in phosphate buffer. The following lipases were used as biocatalysts: Novozyme 435 (Candida antarctica), Amano PS (Burkholderia cepacia) and lipase from Candida cylindracea. All isomers of alcohols were obtained with at least 96% ee.
- Winska, Katarzyna,Grudniewska, Aleksandra,Chojnacka, Anna,Bialonska, Agata,Wawrzenczyk, Czeslaw
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experimental part
p. 670 - 678
(2010/08/07)
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- A study of Heck cyclization reactions to form phenanthridine ring systems
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A survey of conditions for the palladium catalyzed intramolecular Heck cyclization of protected amines has shown that the Herrmann-Beller palladacycle can be exploited under 'cationic' conditions to provide a robust and rapid route (2 h) to the synthesis
- Donaldson, Lauren R.,Haigh, David,Hulme, Alison N.
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p. 4468 - 4477
(2008/09/20)
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- Benzene, Pyridine, and Pyridazine Derivatives
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Disclosed are compounds and pharmaceutically acceptable salts of Formula I wherein A, Q1, Q2, Q3, R31, and R41 are as defined herein. Compounds of Formula I are useful in the treatment of diseases and
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Page/Page column 50
(2008/12/05)
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- SUBSTITUTED TETRALINS AS SELECTIVE ESTROGEN RECEPTOR-BETA AGONISTS
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The present invention relates to novel tetralin ER-β agonist compounds, pharmaceutical compositions thereof, and use of these compounds to treat a ER-β mediated disease such as nocturia, obstructive uropathy, benign prostatic hypertrophy, obesity, dementia, hypertension, incontinence, colon cancer, prostate cancer, infertility, depression, leukemia, inflammatory bowel disease, and arthritis.
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Page/Page column 47-48
(2008/06/13)
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- PYRAZOLO-QUINAZOLINE DERIVATIVES,PROCESS FOR THEIR PREPARATION AND THEIR USE AS KINASE INHIBITORS
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Pyrazolo-quinazoline derivatives of formula (Ia) or (Ib) as defined in the specification, and pharmaceutically acceptable salts thereof, process for their preparation and pharmaceutical compositions comprising them are disclosed; the compounds of the invention may be useful, in therapy, in the treatment of diseases associated with a disregulated protein kinase activity, like cancer.
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Page 31; 86-87
(2008/06/13)
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- A convergent construction of quaternary centres and polycyclic structures
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Various xanthates, made by conjugate addition of xanthic acid to electrophilic olefins, add in a inter- or intra-molecular fashion to olefins allowing a direct introduction of a quaternary centres and the construction of polycyclic structures.
- Binot, Gre?gori,Quiclet-Sire, Be?atrice,Saleh, Twana,Zard, Samir Z.
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p. 382 - 386
(2007/10/03)
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- New oxidative demetalation protocol for molybdenum π-complexes: Enantiocontrolled synthesis of unsaturated ketones and lactones
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An efficient and general oxidative demetalation of (η3-allyl)molybdenum complexes using pyridinium dichromate allows the introduction of a carbonyl group at an allylic terminus of the π-system. The process takes place with high regiocontrol and can lead to the preparation of unsaturated ketones and lactones of high enantiopurity.
- Alcudia, Ana,Arrayas, Ramon Gomez,Liebeskind, Lanny S.
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p. 5773 - 5778
(2007/10/03)
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- A facile cleavage of ketone N,N-dimethylhydrazones by CeCl3·7H2O-SiO2
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Ketone N,N-dimethylhydrazones are rapidly and chemoselectively deprotected to the corresponding ketones in high yields by CeCl3·7H2O supported on silica gel under microwave irradiation. The method is compatible with acid sensitive substrates.
- Yadav,Subba Reddy,Reddy,Sabitha
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p. 1134 - 1136
(2007/10/03)
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- Non-steroid progesterone receptor agonist and antagonist and compounds and methods
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Non-steroidal compounds which are high affinity, high specificity ligands for progesterone receptors are disclosed. The compounds include synthetic derivatives of cyclocymopol and its diastereomers, spectroscopically and chromatographically pure (3R)-cyclocymopol monomethyl ether, which functions as a progesterone receptor antagonist, and spectroscopically and chromatographically pure (3S)-cyclocymopol monomethyl ether, which functions as a progesterone receptor agonist. Also disclosed are methods for employing the disclosed compounds for modulating processes mediated by progesterone receptors and for treating patients requiring progesterone receptor agonist or antagonist therapy.
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- Non-steroid androgen receptor antagonist compounds and methods
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Non-steroidal compounds which are high affinity, high specificity ligand antagonists for the androgen receptor are disclosed. Also disclosed are methods for employing the disclosed compounds for modulating processes mediated by the androgen receptor and for treating patients requiring androgen receptor antagonist therapy.
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- The first total synthesis of (±)-demethyl salvicanol
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Demethyl salvicanol, a novel rearranged 9(10 → 20)-abeo-8, 11, 13-triene diterpene, has been synthesized for the first time. The zinc-promoted coupling reaction of benzyl bromide with ketone and the alkylation of ketone with iodide are the key steps.
- Wang, Xuechao,Pan, Xinfu,Cui, Yuxin,Chen, Yaozu
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p. 10659 - 10666
(2007/10/03)
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- An efficient procedure for palladium-catalyzed reduction of aryl/enol triflates
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An efficient procedure to deoxygenate phenols and enols via trifluoromethanesulfonates is presented. Their reduction with triethylsilane in the presence of a catalytic amount of palladium acetate and bidentate phosphine ligands such as 1,3-bis(diphenylphosphino)propane or 1,1'-bis(diphenylphosphino)ferrocene proceeds efficiently to afford a variety of aromatic, heteroaromatic, and olefinic compounds.
- Kotsuki,Datta,Hayakawa,Suenaga
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p. 1348 - 1350
(2007/10/02)
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- TOTAL SYNTHESIS OF THE ELEMANOLIDES (+/-) ZEMPOALIN A AND B
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Starting with a suitable trisubstituted cyclohexanone derivative two further substituents were introduced via an epoxy ketone which after reduction was reacted with the diethylaluminium derivative of ethoxyacetylene.The resulting dihydroxyester afforded t
- Bartel, S.,Bohlmann, F.
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p. 685 - 688
(2007/10/02)
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- STUDIES ON THE REDUCTION OF CYCLIC 1,3-DIKETONES VIA THEIR TRIFLATES
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Using 1,3-Cyclohexadione (1) and 5,5-dimethyl-1,3-Cyclohexadione (11) as examples, it is shown that 1,3-diketones can be transformed into monoketones, monoalcohols, alkanes and unsaturated ketones.
- Martinez, A. Garcia,Alvarez, R. Martinez,Casado, M. Madueno,Subramanian, L. R.,Hanack, M.
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p. 275 - 280
(2007/10/02)
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- SYNTHESIS OF CEDRANOID SESQUITERPENES. III. FUNCTIONALIZATION AT CARBON 4
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Dimethyl 6,6-dimethyl-5,7-dioxobicyclooct-2-ene-2,3-dicarboxylate (8) on irradiation in acetophenone gives dimethyl 6,6-dimethyl-4,7-dioxotricyclo2,8>octane-1,8-dicarboxylate (13), which on treatment with lithium dimethyl cuprate followed by monodecarbomethoxylation gives methyl 4,4-endo-8-trimethyl-3,6-dioxo-cis-bicyclooctane-1-carboxylate (17).Similar irradiation of dimethyl 4,6,6-trimethyl-5,7-dioxobicyclooct-2-ene-2,3-dicarboxylate (24) and its 7,7-ethylenedioxy derivative (25) followed by treatment with DBU and concentrated H2SO4, respectively, gives dimethyl 3-hydroxy-4,4,8-trimethyl-6-oxo-cis-bicyclo-octa-2,7-diene-1,2-dicarboxylate (30).This, on acetylation, reduction with NaBH4/CeCl3, methanolysis, monodecarbomethoxylation, and hydrogenation, gives methyl endo-6-hydroxy-4,4-endo-8-trimethyl-3-oxo-cis-bicyclooctane-1-carboxylate (38), while on reduction with Li/NH3 followed by monodecarbomethoxylation it gives a methyl 6-hydroxy-4,4-exo-8-trimethyl-3-oxo-cis-bicyclooctane-1-carboxylate (33).
- Yates, Peter,Burnell, D. Jean,Freer, Vernon J.,Sawyer, Jeffery F.
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- Mechanism of Cyclopentene-1-carboxaldehyde Formation by Ring Contraction of 2,3-Epoxycyclohexanols. Improved Synthetic Procedures
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Complete analysis of the reaction mixtures from lithium bromide induced skeletal rearrangement of cis- and trans-1-deuterio-4,4-dimethyl-2,3-epoxycyclohexanol (4d and 7d) showed that the formation of specifically deuterated 5,5- and 3,3-dimethylcyclopente
- Bergman, Rolf,Magnusson, Goeran
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p. 212 - 217
(2007/10/02)
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- Reduction of Vinylogous Thioesters with Lithium Aluminum Hydride. I. Reduction of β-Phenylthio-α,β-unsaturated Cyclic Ketones
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5,5,Dimethyl-3-phenoxy-2-cyclohexenone (Ib) was reduced with lithium aluminum hydride (LAH) to give the 1,2-addition product (IIIa). 2-Methyl-3-phenoxy-2-cyclopentetnone (IIa) gave a mixture of the allyl alcohol (IVa) and 1,2-addition product (IVb).On the
- Matoba, Katsuhide,Tokizawa, Minoru,Morita, Takashi,Yamazaki, Takao
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p. 368 - 372
(2007/10/02)
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- Insect Growth Regulators. XVI Syntheses of Juvenoids with the 3,3-Dimethylcyclohexane System.
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New cyclic juvenoids containing the 3,3-dimethylcyclohexane (esters 16, 18, 22, 26, and ehters 28a,b) or the 5,5-dimethyl-2-cyclohexene system (esters 15, 17, 21, 25, and ehters 27a,b) have been obtained by a several-step synthesis starting from dimedone (1).The compounds obtained exhibited morphogenetic activity against larvae of Dysdercus cingulatus and they were inactive on pupae of Tenebrio molitor.Keywords: Claisen rearrangement; gem-Dimethylcyclohexane derivatives; Juvenoids
- Wawrzenczyk, Czeslaw,Lochynski, Stanislaw
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- A FACILE METHOD FOR REGIOSELECTIVE 1,2-CARBONYL TRANSPOSITION OF Δ2-CYCLOHEXENONE SYSTEMS LEADING TO THE POSITIONALLY ISOMERIC Δ2-CYCLOHEXENONES
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A new, facile procedure is described which allows the regioselective 1,2-carbonyl transposition of Δ2-cyclohexenone systems leading to the positionally isomeric Δ2-cyclohexenones.The scope and limitation of the method is presented.
- Mimura, Tetsuya,Nakai, Takeshi
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p. 1099 - 1102
(2007/10/02)
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- Preparation of a 5-(2,2-dihalovinyl)-4,4-dimethyl-2-oxotetrahydrofuran
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A process for preparing a 5-(2,2-dihalovinyl)-4,4-dimethyl-2-oxotetrahydrofuran of formula: STR1 wherein X and Z are each either chlorine or bromine, which comprises the step of treating a compound of formula: STR2 with an excess of a base selected from alkali metal hydroxides and chemical equivalents thereof.
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