Search results for " Synthesis"
showing 10 items of 1625 documents
The quantitative determination of metabolites of 6-mercaptopurine in biological materials. VII. Chemical synthesis by phosphorylation of 6-thioguanos…
1990
Abstract A fast and reliable two-step method has been established for the chemical synthesis of 6-thioguanosine 5′-monophosphate, 6-thioguanosine 5′-diphosphate and 6-thioguanosine 5′-triphosphate starting from the ribonucleoside. In the first step, 6-thioguanosine dissolved in triethyl phosphate, at high yield reacts with phosphorus oxide trichloride to 6-thioguanosine 5′-monophosphate which is purified by anion-exchange chromatography on DEAE-Sephadex using a step gradient of hydrochloric acid. In the second step, 6-thioguanosine 5′-monophosphate dissolved in water, reacts with phosphoric acid in the presence of pyridine/dicyclohexyl carbodiimide and is converted to 6-thioguanosine 5′-dip…
Catalytic Enantioselective Conjugate Alkynylation of β-Aryl-β-trifluoromethyl Enones Constructing Propargylic All-Carbon Quaternary Stereogenic Cente…
2016
The enantioselective conjugate alkynylation of β-aryl-β-trifluoromethyl enones has been carried out using terminal alkynes and diethylzinc in the presence of 3,3'-bis(perfluorophenyl)BINOL as the chiral ligand to give the corresponding ketones bearing a trifluoromethylated propargylic quaternary stereocenter with fair to good enantioselectivities. Enones bearing a bulky 2-naphthyl attached to the carbonyl group provided the best enantioselectivities. The synthetic applicability of the resulting products has been demonstrated with their iodocyclization to form 4H-pyrans.
Enantioselective Synthesis of 5-Trifluoromethyl-2-oxazolines under Dual Silver/Organocatalysis.
2019
[EN] The first enantioselective formal [3 + 2] cycloaddition between ¿-isocyanoesters and trifluoromethylketones to give 5-trifluoromethyl-2-oxazolines bearing two contiguous stereogenic centers, one of them being a quaternary stereocenter substituted with a CF3 group, has been developed. The reaction is based upon a multicatalytic approach that combines a bifunctional Brønsted base-squaramide organocatalyst and Ag+ as Lewis acid. The reaction could be achieved with a range of aryl and heteroaryl trifluoromethyl ketones, and the resulting oxazolines were obtained with good to excellent diastereo- and enantioselectivity.
Mg/BOX complexes as efficient catalysts for the enantioselective Michael addition of malonates to β-trifluoromethyl-α,β-unsaturated ketones and their…
2021
Abstract Magnesium (II)-BOX complexes catalyze the enantioselective Michael addition of malonates to β-trifluoromethyl enones and their N-sulfonyl imines to give ketones or (E)-enamines bearing a trifluoromethylated stereogenic center, respectively, with good yields and high enantiomeric excesses. Magnesium complexes proved to be more active and stereoselective than zinc and copper analogues in these reactions.
Copper-catalysed enantioselective Michael addition of malonic esters to β-trifluoromethyl-α,β-unsaturated imines
2017
[EN] Copper triflate-BOX complexes catalyse the enantioselective conjugate addition of methyl malonate to beta-trifluoromethyl-alpha,beta-unsaturated imines to give the corresponding enamines bearing a trifluoromethylated stereogenic centre with good yields, and diastereo- and enantioselectivities. The usefulness of the method has been shown with the synthesis of optically active beta-trifluoromethyl delta-amino esters and optically active trifluoromethyl piperidones.
Catalytic Enantioselective Conjugate Alkynylation of α,β-Unsaturated 1,1,1-Trifluoromethyl Ketones with Terminal Alkynes.
2016
The first catalytic enantioselective conjugate alkynylation of α,β-unsaturated 1,1,1-trifluoromethyl ketones has been carried out. Terminal alkynes and 1,3-diynes were treated with trifluoromethyl ketones in the presence of a low catalytic load of a CuI-MeOBIPHEP complex (2.5 mol %) and triethylamine (10 mol %) to give the corresponding trifluoromethyl ketones bearing a propargylic stereogenic center at the β position with good yields and excellent enantiomeric excesses in most of the cases. No 1,2-addition products were formed under the reaction conditions. The procedure showed broad substrate scope for alkyne, diyne, and enone. A rationale for the observed stereochemistry has been provide…
Diarylprolinol as a Ligand for Enantioselective Alkynylation of Cyclic Imines
2017
An easily accessible prolinol derived ligand, (S)-bis(3,5-bis(trifluoromethyl)phenyl)(pyrrolidin-2-yl)methanol, has been efficiently applied in the catalytic enantioselective addition of terminal alkynes to cyclic imines using dimethylzinc (Me2Zn) under mild reaction conditions. The developed catalytic system led to chiral propargylic sulfamidates with high yields (up to 97%) and excellent enantioselectivities (up to 97% ee).
Enantioselective Zirconium-Catalyzed Friedel−Crafts Alkylation of Pyrrole with Trifluoromethyl Ketones
2009
The first catalytic enantioselective Friedel-Crafts alkylation of pyrrole with 2,2,2-trifluoroacetophenones to give pyrroles with a trifluoromethyl-substituted tertiary alcohol moiety bearing a quaternary stereogenic center is described. The reaction is achieved in the presence of a 3,3'-dibromo-BINOL-Zr(IV) complex to give the expected products with high yields (up to 98%) and good enantioselectivities (up to 93% ee). The absolute stereochemistry of the products has been determined by chemical correlation.
Catalytic asymmetric conjugate addition of terminal alkynes to β-trifluoromethyl α,β-enones.
2014
The first enantioselective conjugate alkynylation of β-trifluoromethyl α,β-enones using terminal alkynes and a taniaphos–Cu(I) complex as catalyst is described. Ketones bearing a trifluoromethylated propargylic chiral centre in the β-position were obtained with good yields and high enantiomeric excesses (up to 99%).
Highly enantioselective copper(I)-catalyzed conjugate addition of 1,3-diynes to a,b-unsaturated trifluoromethyl ketones
2015
[EN] The conjugate diynylation of a,b-unsaturated trifluoromethyl ketones is carried out in the presence of a low catalytic load (2.5 mol%) of a copper(I)–MeOBIPHEP complex, triethylamine and a terminal 1,3-diyne. Pre-metalation of the terminal 1,3-diyne with stoichiometric or higher amounts of dialkylzinc reagent is not required. The corresponding internal diynes bearing a propargylic stereogenic center are obtained with good yields and excellent enantioselectivities.