14398-35-7Relevant academic research and scientific papers
New Approach to the Synthesis of the Natural Product Aripuanin
Lazaro, Aline S.,Ribeiro, Pedro H. Zana,Sairre, Mirela I.,Donate, Paulo M.
supporting information, p. 1374 - 1378 (2015/05/26)
Aripuanin is a megastigmane that exists in the leaves of Ficus aripuanensis C.C. Berg (Moraceae). The present study describes a new approach to the total synthesis of this natural product starting from the readily available β-ionone. The proposed syntheti
Synthesis and in vitro characterization of ionone-based compounds as dual inhibitors of the androgen receptor and NF-κB
Liu, Weiguo,Zhou, Jinming,Geng, Guoyan,Lin, Rongtuan,Wu, Jian Hui
, p. 227 - 234 (2014/04/03)
Current therapeutic strategy for advanced prostate cancer is to suppress the androgen receptor (AR) signaling. However, lethal castration-resistant prostate cancer (CRPC) arises due to AR reactivation via multiple mechanisms, including mutations in the AR and cross-talk with other pathways such as NF-κB. We have previously identified two ionone-based antiandrogens (SC97 and SC245), which are full antagonists of the wild type and the clinically-relevant T877A, W741C and H874Y mutated ARs. Here, we discovered SC97 and SC245 also inhibit NF-κB. By synthesizing a series of derivatives of these two compounds, we have discovered a novel compound 3b that potently inhibits both AR and NF-κB signalling, including the AR F876L mutant. Compound 3b showed low micromolar antiproliferative activites in C4-2B and 22Rv1 cells, which express mutated ARs and are androgen-independent, as well as DU-145 and PC-3 cells, which exhibit constitutively activated NF-κB signalling. Our studies indicate 3b is effective against the CRPC cells.
Synthesis, olfactory evaluation, and determination of the absolute configuration of the 3,4-didehydroionone stereoisomers
Serra, Stefano,Fuganti, Claudio,Brenna, Elisabetta
, p. 1110 - 1122 (2007/10/03)
The synthesis of 3,4-didehydroionone isomers 4, (+)-6, and (-)-6 and of 3,4-didehydro-7,8-dihydroionone isomers 5, (+)-7, and (-)-7 was accomplished starting from commercially available racemic α-ionone (1). Their preparation of the racemic forms 4-7 was first achieved by mean of a number of chemo- and regioselective reactions (Schemes 1 and 2). The enantio- and diastereoselective lipase-mediated kinetic acetylation of 4-hydroxy-γ- ionone (10a/10b) provided 4-hydroxy-γ-ionone (+)-10a/(±)-10b and (+)-4-(acetyloxy)-γ-ionone ((+)12b) (Scheme 3). The latter compounds were used as starting materials to prepare the 3,4-didehydro-γ-ionones (+)- and (-)-6 and the 3,4-didehydro-7,8-dihydro-γ-ionones (+)- and (-)-7 in enantiomer-enriched form. The absolute configuration of (+)-12b was determine by chemical correlation with (+)-(6S)-γ-ionone ((+)-3) and with (-)-(6S)-α-ionone ((-)-1) therefore allowing to assign the (S)-configuration to (+)-6 and (+)-7. Olfactory evaluation of the above described 3,4-didehydroionone isomers shows a significant difference between the enantiomers and regioisomers both in fragrance feature and in detection threshold (Table).
Synthesis of biotinylated retinoids for cross-linking and isolation of retinol binding proteins
Nesnas, Nasri,Rando, Robert R,Nakanishi, Koji
, p. 6577 - 6584 (2007/10/03)
The synthesis of (3R)-3-[Boc-Lys(biotinyl)-O]-11-cis-retinol bromoacetate and 3-[Boc-Lys(biotinyl)-O]-all trans-retinol chloroacetate is described. These biotinylated retinoids are instrumental in labeling the retinol binding proteins (RBPs) via a nucleophilic displacement of the haloacetate by a residue in the binding site of the protein. The covalently linked biotin will allow for a facile isolation and purification of the protein on a streptavidin column thus rendering the protein ready for a tryptic digest followed by mass spectrometric analysis. The 11-cis retinoid was synthesized via metal reduction of an alkyne intermediate generated from a Horner-Wadsworth-Emmons (HWE) reaction whereas the all-trans was synthesized via two consecutive HWE couplings.
Syntheses of theaspirone and vitispirane via palladium(II)-catalyzed oxaspirocyclization
Nilsson, Ylva I. M.,Aranyos, Attila,Andersson, Pher G.,Baeckvall, Jan-E.,Parrain, Jean-Luc,Ploteau, Christelle,Quintard, Jean-Paul
, p. 1825 - 1829 (2007/10/03)
Total syntheses of theaspirone (A and B) and vitispirane (A and B) are described. The key step in the syntheses is the palladium(II)-catalyzed intramolecular oxaspirocyclization of diene alcohol 4 to either vitispirane or the allylic alcohol 9. The outcome of the oxaspirocyclization is very much dependent on the solvent employed. In water-acetic acid (4:1) a 1:1 mixture of the diastereomeric alcohols 9A and 9B was exclusively formed. In water with 8 equiv of a strong non-nucleophilic acid, vitispiranes A and B (1:1) were obtained. An alternative procedure to obtain vitispirane with the use of LiCl and K2CO3 is described. In the latter reaction vitispirane B is formed preferentially. This result is explained by an equilibrium between the two possible π-allyl complexes 5A and 5B, the kinetically favored 5B being transformed into vitispirane 3B before isomerization to 5A occurs.
New hindered isomers of 3-dehydroretinal (Vitamin A2)
Chen, Rong-Liang,Liu, Robert S.H.
, p. 7809 - 7816 (2007/10/03)
The preparation of six new isomere (7-cis, 7,9-dicis, 7,11-dicis, 7,13-dicis, 7,9,11-tricis and 7,9,13-tricis) of 3-dehydroretinal (1, vitamin A2), and their spectroscopic properties are reported. Because of the unexpected 1,7-H migration in photo-sensitized isomerization of the smaller building blocks in the dehydro-series, the introduction of the 7-cis geometry in the synthesis of new hindered isomers of 3-dehydroretinal required construction of this cis-double bond prior to that of the 3,4-double bond. Copyright
Palladium-catalyzed oxaspirocyclizations
Andersson,Nilsson,Backvall
, p. 559 - 572 (2007/10/02)
Palladium-catalyzed oxidation of 1-(3-hydroxyalkyl) and 1-(4- hydroxyalkyl)-1,3-cycloalkadienes results in a stereocontrolled oxaspirocyclization. The reaction proceed via a spirocyclic (π- allyl)palladium intermediate, which is attacked by an acetate or a chloride nucleophile leading to an overall 1,4-addition across the diene. The intermediate (π-allyl) palladium complex was independently prepared and characterized. The stereochemistry of the 1,4-addition can be controlled to give either cis or trans 1,4-addition across the double bonds. The oxaspirocyclization was applied to the total synthesis of theaspirone.
Synthesis of (±)-E-4-(1,2,4-trihydroxy-2,6,6-trimethylcyclohexyl)-but-3-en-2-one: A novel degraded carotenoid isolated from New Zealand thyme (Thymus vulgaris) honey
Broom,Ede,Wilkins
, p. 3197 - 3200 (2007/10/02)
A racemic synthesis of the title compound is described starting from β-ionone. The key steps involve selective hydroboration of a triene, followed by molybdenum mediated epoxidation of the resulting homoallylic alcohol with subsequent ring opening of the epoxide to give the title compound.
