16821-32-2Relevant academic research and scientific papers
Novel transformation of methoxy tetralones during demethylation with boron trifluoride etherate and acetic anhydride
Banerjee, Ajoy K.,Bedoya, Liadis,Vera, William J.,Melean, Carlos,Mora, Henry,Laya, Manuel S.,Alonso, Miguel
, p. 3399 - 3408 (2004)
Tetralones 3 and 9 on treatment with a mixture of boron trifluoride etherate and acetic anhydride underwent molecular transformations yielding the fully aromatized products 6 and 10, respectively, Oxidation of dimethoxy tetralin 13 with chromic acid and acetic acid afforded 6-methoxy-α- tetralone 12.
An Attempted Synthesis of Tricyclo1,10.01,7.04,10>-1(7),4(10)-dodecadiene
McMurry, John E.,Swenson, Rolf
, p. 3209 - 3212 (1987)
Titanium-induced cyclization of diketone 4 yields diene 12, presumably by Cope rearrangement of the desired tricyclo1,10.01,7.04,10>-1(7),4(10)-dodecadiene (1).Molecular mechanics calculations support the belief that the rearrangement should be rapid.
Ru-catalyzed mechanochemical asymmetric transfer hydrogenations in aqueous media using chitosan as chirality source
Kolcsár, Vanessza Judit,Sz?ll?si, Gy?rgy
, (2022/02/09)
As the demand for sustainable methods increases, synthetic chemistry is focusing on the application of environmentally benign methods, such as fast reactions induced by alternative energy transmission. Chitosan is a chiral biopolymer of natural origin, which can be used in asymmetric catalysis. The application of Ru-chitosan complexes along with the mechanochemical activation may open great opportunities for sustainable preparation of optically pure alcohols. In the present study, we optimized the mechanochemical asymmetric transfer hydrogenation of 4-chromanone, carried out in a mixing mill. The reaction was catalyzed by the in situ formed Ru-chitosan complex, applying HCOONa as the hydrogen donor in aqueous media. We examined the mechanical effects of different grinding media sizes, then explored the scope of the system using 24 prochiral ketones, which ranged from hetero- and carbocyclic ketones to acetophenone derivatives. In most of the cases, the reactions were successfully scaled up to 1 mmol and the products were isolated in good yields and outstanding enantioselectivities. Our present study is a significant step forward to the development of environmentally benign and sustainable enantioselective processes, as the alternative activation method provided optically enriched alcohols using a biodegradable chirality source in aqueous media.
Design of Ru(II)-NHC-Diamine Precatalysts Directed by Ligand Cooperation: Applications and Mechanistic Investigations for Asymmetric Hydrogenation
Daniliuc, Constantin G.,Glorius, Frank,Hellmann, Lars,Li, Wei,Mück-Lichtenfeld, Christian,Neugebauer, Johannes,Wagener, Tobias
supporting information, p. 7100 - 7107 (2020/05/18)
A modular synthesis of Ru(II)-NHC-diamine complexes from readily available chiral N-heterocyclic carbenes (NHCs) and chiral diamines is disclosed for the first time. The well-defined Ru(II)-NHC-diamine complexes show unique structure and coordination chem
Green Organic Solvent-Free Oxidation of Alkylarenes with tert-Butyl Hydroperoxide Catalyzed by Water-Soluble Copper Complex
Ajjou, Abdelaziz Nait,Rahman, Ateeq
, p. 165 - 174 (2020/04/15)
Different benzylic compounds were efficiently oxidized to the corresponding ketones with aqueous 70% tert-butyl hydroperoxide (TBHP) and the catalytic system composed of CuCl2.2H2O and 2,2'-biquinoline-4,4'-dicarboxylic acid dipotassium salt (BQC). The catalytic system CuCl2/BQC/TBHP allows obtaining high yields at room temperature under organic solvent-free conditions. The interest of this system lies in its cost effectiveness and its benign nature towards the environment. Benzylic tertbutylperoxy ethers and benzylic alcohols were observed and suggested as the reaction intermediates. Analysis of organic products by atomic absorption did not show any contamination with copper metal. In terms of efficiency, CuCl2/BQC system is comparable or superior to the most of the catalytic systems described in the literature and which are based on toxic organic solvent.
Deoxyfluorination with CuF2: Enabled by Using a Lewis Base Activating Group
Bode, Bela E.,Chabbra, Sonia,Champion, Sue,Dawson, Daniel M.,Sood, D. Eilidh,Sutherland, Andrew,Watson, Allan J. B.
supporting information, p. 8460 - 8463 (2020/04/10)
Deoxyfluorination is a primary method for the formation of C?F bonds. Bespoke reagents are commonly used because of issues associated with the low reactivity of metal fluorides. Reported here is the development of a simple strategy for deoxyfluorination, using first-row transition-metal fluorides, and it overcomes these limitations. Using CuF2 as an exemplar, activation of an O-alkylisourea adduct, formed in situ, allows effective nucleophilic fluoride transfer to a range of primary and secondary alcohols. Spectroscopic investigations have been used to probe the origin of the enhanced reactivity of CuF2. The utility of the process in enabling 18F-radiolabeling is also presented.
PERIPHERAL ALKYL AND ALKENYL CHAINS EXTENDED BENZENE DERIVATIVES AND PHARMACEUTICAL COMPOSITION INCLUDING THE SAME
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Paragraph 0063; 0502-0505, (2020/10/20)
The compounds represented by Formula (I), which are peripheral alkyl and alkenyl chains extended benzene derivatives, are useful as dual autotaxin (ATX) / histone deacetylase (HD AC) inhibitors. These compounds may be included in a pharmaceutical composition along with a pharmaceutically acceptable carrier, and be used in a therapeutically effective amount for prophylaxis or treatment of various diseases and disorders.
Visible-Light-Triggered C-C and C-N Bond Formation by C-S Bond Cleavage of Benzylic Thioethers
Lanzi, Matteo,Merad, Jérémy,Boyarskaya, Dina V.,Maestri, Giovanni,Allain, Clémence,Masson, Géraldine
supporting information, p. 5247 - 5250 (2018/09/13)
The cleavage of sulfidic C-S bonds under visible-light irradiation was harnessed to generate carbocations under neutral conditions and synthesize valuable di- and triarylalkanes as well as benzyl amines. To this end, photoredox catalysis and direct photoinduced C-S bond cleavage are used as complementary approaches and participate in the versatility of the general strategy. Extensive mechanistic studies have demonstrated the diversity of the reaction mechanism at work in these different reactions.
11a-N-tosyl-5-carbapterocarpans: Synthesis, antineoplastic evaluation and in silico prediction of ADMETox properties
Mendes, Joseane A.,Salustiano, Eduardo J.,Pires, Carulini de S.,Oliveira, Thaís,Barcellos, Julio C.F.,Cifuentes, Jhonny M.C.,Costa, Paulo R.R.,Rennó, Magdalena N.,Buarque, Camilla D.
, p. 585 - 590 (2018/07/29)
11a-N-tosyl-5-carbapterocarpans (5a–c and 6a–c), 9-N-tosyl-4,4a,9,9a-tetrahydro-3H-carbazole (7), 11a-N-tosyl-5-carbapterocarpen (8) analogues of LQB-223 (4a), were synthesized through palladium catalyzed azaarylation of substituted dihydronaphtalenes (14a–c) and cyclohexadiene (15), respectively, with N-tosyl-o-iodoaniline (11). In order to understand the role of the N-tosyl moiety for the pharmacological activity, the azacarbapterocarpen (9) was also synthesized by Fischer indol reaction. The structural requirements at the A and D-rings for the antineoplastic activity toward human leukemias and breast cancer cells were evaluated as well. Substitutions on the A-ring of 4a and analogues alter the effect on different breast cancer subtypes. On the other hand, A-ring is not essential for antileukemic activity since compound 7, which does not contain the A-ring, showed efficacy with high selectivity indices for drug-resistant leukemias. On the other hand, substitutions on the D-ring of 4a for fluorine or iodine did not improve the antileukemic activity. In silico studies concerning Lipinskís rule of five, ADMET properties and drug scores of those compounds were performed, indicating good physicochemical properties for all compounds, in special for compound 7.
(Poly)cationic λ3-Iodane-Mediated Oxidative Ring Expansion of Secondary Alcohols
Walters, Jennifer C.,Tierno, Anthony F.,Dubin, Aimee H.,Wengryniuk, Sarah E.
supporting information, p. 1460 - 1464 (2018/04/06)
Herein, a simplified approach to the synthesis of medium-ring ethers through the electrophilic activation of secondary alcohols with (poly)cationic λ3-iodanes (N-HVIs) is reported. Excellent levels of selectivity are achieved for C–O bond migration over established α-elimination pathways, enabled by the unique reactivity of a novel 2-OMe-pyridine-ligated N-HVI. The resulting hexafluoroisopropanol (HFIP) acetals are readily derivatized with a range of nucleophiles, providing a versatile functional handle for subsequent manipulations. The utility of this methodology for late-stage natural product derivatization was also demonstrated, providing a new tool for diversity-oriented synthesis and complexity-to-diversity (CTD) efforts. Preliminary mechanistic investigations reveal a strong effect of alcohol conformation on the reactive pathway, thus providing a predictive power in the application of this approach to complex molecule synthesis.
