Kinetic resolutions and kinetic asymmetric transformations (KAT) as well as dynamic kinetic resolutions and dynamic kinetic asymmetric transformations (DYKAT) are important synthetic protocols. The feasibility of KAT and DYKAT processes for asymmetric allylic alkylations (AAA) is explored utilizing a single substrate--conduritol B tetraesters. Both processes can be performed resulting in excellent enantioselectivity. The impact of nucleophile and leaving group on the effectiveness of each is outlined. The ability to differentiate the various hydroxyl groups is also described. For this purpose, 4-tert-butyldimethylsiloxy-2,2-dimethylbutyric acid was developed as a nucleophile. The utility of effecting KAT/DYKAT processes through the Pd-catalyzed AAA reaction is demonstrated by efficient syntheses of both enantiomers of the potent glycosidase inhibitor cyclophellitol.
A new technique for determining the volumetric unfrozen water content of frozen soils is reported, which uses time domain reflectometry (TDR) to measure the dielectric property. Using precise temperature control, the technique, which was developed previously by others for unfrozen soils, has been successfully applied to the measurement of unfrozen water contents of frozen soils. Curves of the dielectric property versus temperature show a close similarity to unfrozen water content curves, for a variety of soils. Results from experiments on ice–water mixtures and from combined TDR–dilatometry experiments on frozen soils suggest that an empirical relationship obtained by Topp, Davis, and Annan may be applicable to frozen media as well as unfrozen soils. Using this relationship, dielectric values were converted to unfrozen water content values, and the results agreed very closely with published data for similar soils, determined by other methods. For silt loams, agreement is typically within ± 1½% in volumetric water content, and for clays ± 3 %. Some of this difference is undoubtedly due to soil sample variations.
A large-scale synthesis of denagliptin tosylate has been developed. The efficiency of the synthesis has been improved from the initially scaled route by changing the order of steps (performing a dehydration at a late stage). The key step of the synthesis is a single-step peptide coupling/dehydration, mediated by n-propanephosphonic acid cyclic anhydride. The challenges of developing this synthesis into a robust and practical manufacturing route are described.
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