Intramolecular Construction of Trifluoromethyl Group by the Palladium-Catalyzed Alkylation of 2,3,3-Trifluoroallylic Carbonates with Indoles.

The palladium-catalyzed alkylation reaction of 2,3,3-trifluoroallylic carbonates with indoles afforded a trifluoromethyl group possessing 3-substituted indole derivatives. The reaction proceeded via attack of the C-3 carbon of the indoles onto the C-2 position of the allylic moiety and intramolecular construction of the trifluoromethyl group by the intramolecular fluorine atom shift from the C-2 position to the C-3 position of the allyl unit.

Palladium-catalyzed amination of 2,3,3-trifluoroallyl esters: synthesis of trifluoromethylenamines via an intramolecular fluorine shift and CF3 group construction.

The palladium-catalyzed reaction of 2,3,3-trifluoroallyl esters with several types of amines afforded trifluoromethylenamines, which were formed by the addition of a nitrogen nucleophile at the C-2 position and the intramolecular construction of the trifluoromethyl group via the fluorine atom shift from the C-2 to the C-3 position.

Palladium-catalyzed double alkylation of 3-aryl-2-fluoroallyl esters with malonate nucleophiles through the carbon-fluorine bond cleavage.

The alkylation of (Z)-3-aryl-2-fluoroallyl acetate with the malonate anion by the [Pd(C3H5)(cod)]BF4/2,2'-bpy catalyst proceeds through the carbon-fluorine bond cleavage, and 2 equiv of the malonate nucleophile was introduced to the allyl substrate.

[Quantitative estimation of preanalytical variables which may influence the determinations of prothrombin time (PT) and activated partial thromboplastin time (APTT)].

Prothrombin time (PT) and activated partial thromboplastin time (APTT) tests principally measure the time for a fibrin clot developed in citrated plasma after activation. For the complexity of chemical reactions, a number of preanalytical variables potentially influence the outcome of results. In the present study, we evaluated some preanalytical variables frequently encountered in clinical settings. The volumes of citrated whole-blood specimens collected from inpatients widely varied from 0.99 ml to 2.90 ml indicating 1.6% of unacceptable rate, whereas none of the specimens from outpatients was out of acceptable range. The citrated whole-blood volume significantly affected the determinations of both PT and APTT; the results indicating the more volume the longer clotting time. Also, whole-blood specimens collected in EDTA2K revealed significantly prolonged PT and APTT values in healthy subjects and the patients with anticoagulant therapy of heparin and of warfarin. Storage conditions, time and temperature might influence the PT and APTT values. In particular, citrated whole-blood specimens stood at room temperature revealed the prolonged clotting time in APTT assay by hours. The effects of other variables evaluated such as a half-volume adjustment, needle gauge or syringe type were negligible. With these results, it was concluded that; first, an accurate venipuncture is critical, particularly venipuncture from patients in wards where many different physicians and nurses are in charge and in changing by days. Secondly, the citrated whole-blood specimens should be assayed quickly without any unnecessary storage at room temperature beyond four hours.