Search results for "stereoselectivity"
showing 10 items of 325 documents
A novel synthetic approach to pyran-2,4-dione scaffold production: Microwave-assisted dimerization, cyclization, and expeditious regioselective conve…
2020
Abstract Here, we report a novel, green, simple, low-cost, and rapid methodology for the high-yield production of pyran-2,4-dione scaffolds under microwave irradiation. Regio- and stereoselective conversions of β-diketone systems into β-enaminones were achieved using 18 primary amines and four amino acid esters. Microwave-assisted further cyclization of 3-(β-substitutedvinyl)-6-phenyl-pyran-2,4-dione into 3-benzoyl-4,7-diphenyl-2H,5H-pyrano[4,3-b]pyran-2,5-dione via reaction with ethyl benzoyl acetate.
Using theozymes for designing transition-state analogs for the intramolecular aldol reaction of δ-diketones
2001
Two theozymes for the intramolecular aldol reaction of δ-diketones have been studied using ab initio methods. The presence of both acid/base residues favors several steps of the aldol reaction. The appropriate positioning of these residues can accelerate one of two diastereromeric reaction pathways, the catalyzed aldol reaction being highly stereoselective. Analysis of the geometrical parameters, charge distribution, and the shape of molecular electrostatic potential for the corresponding acid/base catalyzed transition structure allows us to design adequate transition-state analogs to favor a reactive channel of this intramolecular aldol reaction. © 2001 John Wiley & Sons, Inc. Int J Quant …
ChemInform Abstract: P-Chirogenic Secondary Phosphine Oxides: New Stereoselective Synthesis and Applications
2015
ChemInform Abstract: Photochemical Transformations of Some Neoclerodane and Labdane Diterpene Ketones.
2010
Some neoclerodane (2–4) and labdane (5 and 6) diterpene ketones having a β- or γ-hydroxy function, an α-epoxy group, or an α-olefinic double bond have been irradiated at λ = 313 nm in dry solvents (benzene or methanol). Fruticolone (2) yielded the naturally occurring 5,6-seco-neoclerodan-6,1α-olide derivative fruticolide (1), while hispanolone (5) gave the δ-lactone 8, both transformations involving a Norrish type I photoreaction. The α,β-unsaturated ketone derivative 4 was transformed into 7 by a stereoselective intramolecular [2+2] cycloaddition reaction involving its furanic 13(16)-double bond. Finally, the α-epoxy ketone 6 was rearranged to the 10(98)abeo-labda-7,9-dione derivative 10. …
ChemInform Abstract: Carbohydrates as Chiral Templates in Stereoselective (4 + 2) Cycloaddition Reactions
2010
The hMTH1 paradox: antioxidants recommended in cancer?
2014
Summary Activated Ras GTPase signalling is a critical driver of oncogenic transformation and malignant disease. Cellular models of RAS-dependent cancers have been used to identify experimental small-molecules, such as SCH51344, but their molecular mechanism of action remains generally enigmatic. Here, using a chemical proteomic approach we identify the target of SCH51344 as the human mutT homologue MTH1, a nucleotide pool sanitising enzyme. Loss-of-function of MTH1 impaired growth of KRAS tumour cells whereas MTH1 overexpression mitigated sensitivity toward SCH51344. Searching for more drug-like inhibitors, we identified the kinase inhibitor crizotinib as a nanomolar suppressor of MTH1 acti…
Stereoselective Synthesis of Bromopiperidinones and their Conversion to Annulated Heterocycles
2009
N-Galactopyranosyl- and N-glucopyranosyl imines of aliphatic, aromatic and heteroaromatic aldehydes react with 1-methoxy-3-trimethylsilyloxy-1,3-butadiene in a domino Mannich-Michael reaction cascade to give 2-substituted 5,6-dehydro-piperidin-4-ones with high diastereoselectivity. Treatment of these cyclic enaminones with N-bromo-succinimide yields the corresponding 2-substituted 5-bromo-5,6-dehydropiperidinones which react with L-SelectrideⓇ or methylcuprate to afford the saturated bromo-piperidinones with high diastereoselectivity. Condensation reactions of these products with thioamides afford thiazolopiperidines
A Stereocontrolled Protocol to Highly Functionalized Fluorinated Scaffolds through a Fluoride Opening of Oxiranes
2016
A novel selective and substrate-dependent synthetic protocol has been developed towards the synthesis of various fluorine-containing, highly functionalized cycloalkane derivatives. The method involves the stereoselective epoxidation of some unsaturated cyclic beta-amino acid derivatives as model compounds, followed by a regioselective fluoride opening of oxiranes under various conditions with Deoxofluor and XtalFluor-E reagents, thereby offering an insight into this new epoxide opening methodology with fluoride.
ChemInform Abstract: Selective “One-Pot” Synthesis of Functionalized Cyclopentenones.
2012
Reaction of squaric acid derivatives with vinyl magnesium bromide followed by treatment with trifluoroethanol allows a new and stereoselective access to functionalized cyclopentenones of type (III)/ (V).
Regio- and stereoselective synthesis of constrained enantiomeric β-amino acid derivatives
2008
Abstract Chlorosulfonyl isocyanate addition to (−)- and (+)-apopinene furnished monoterpene-fused β-lactams in highly regio- and stereospecific reactions. β-Lactams 5 and 13 exhibited reactivities similar to those of the cycloalkane-fused analogs and were easily converted to the β-amino acid and its protected derivatives. The base-catalyzed isomerization of the cis -amino ester afforded the corresponding trans -amino acid enantiomers in excellent yields. The complete isomerization is explained by the stability difference, which was estimated by ab initio calculations between the cis- and trans -diastereomers.