Dramatic switching of protein kinase C agonist/antagonist activity by modifying the 12-ester side chain of phorbol esters

A dramatic switching of PKC agonist and antagonist activity was observed by modification of the hydrophilicity of the 12-ester side chain of phorbol. Thus, phorbol ester 4 that contains a glycol at the 12-ester chain demonstrated a pure and significant antagonist ability of PKC; however, 3 that contains an alkanol at the 12-ester chain demonstrated a potent PKC agonist activity. On the basis of the structural difference between 3 and 4 and results of the partition assay in the Hela cell/PBS buffer system, we propose that 4 acts as a translocation poison of the PKC-phorbol ester complex. The approach of controlling the agonist/antagonist activity of phorbol esters by the nature (i.e., hydrophilicity, charge, and rigidity, etc.) of the 12-ester chain may be very useful for developing selective PKC inhibitors and a potential pharmaceutical compound for anticancer therapies.     

Rhodium-catalyzed reformatsky-type reaction

A novel Reformatsky-type reaction was developed using RhCl(PPh(3))(3) and diethylzinc. Inter- and intramolecular Reformatsky-type reactions were achieved efficiently under mild reaction conditions to give beta-hydroxy esters.     

Assembly state of catalytic modules as chiral switches in asymmetric Strecker amino acid synthesis

Self-assembled chiral polymetallic complexes often demonstrate novel properties as asymmetric catalysts. We report the three-dimensional structures of two such asymmetric catalysts (crystals A and B) for Strecker alpha,alpha-disubstituted amino acid synthesis. These complexes are constructed via assembly of the same chiral modules derived from d-glucose, but their assembly modes differ. The enantioselectivity in the Strecker reaction was dramatically switched, depending on which assembly mode was used: the catalyst generated in situ whose structure is represented by crystal B, or by crystal A. These findings provide insight into the functional importance of higher-order structures of an artificial catalyst.     

Target structure induced suppression of the ionization cross section for very low energy antiproton-hydrogen collisions

Low energy antiprotons have been used previously to give benchmark data for theories of atomic collisions. Here we present measurements of the cross section for single, nondissociative ionization of molecular hydrogen for impact of antiprotons with kinetic energies in the range 2-11 keV, i.e., in the velocity interval of 0.3-0.65 a.u. We find a cross section which is proportional to the projectile velocity, which is quite unlike the behavior of corresponding atomic cross sections, and which has never previously been observed experimentally.     

Effect of optical purity on the critical heat capacity at the smectic-A-(chiral)-smectic-C transition in an antiferroelectric liquid crystal

High resolution ac calorimetric measurements have been carried out near the smectic-A-chiral-smectic-C phase transition in the antiferroelectric liquid crystal 4-(1-methylheptyloxycarbonyl)phenyl 4(')-octyloxybiphenyl-4-carboxylate (MHPOBC). Data on samples with different optical purities have been analyzed in detail using a renormalization-group expression with corrections-to-scaling terms. The chiral-smectic-C(alpha)-chiral-smectic-C phase transition is first order, while the smectic-A-chiral-smectic-C(alpha) phase transition is second order. A direct smectic-A-chiral-smectic-C phase transition, which occurs in near-racemic mixtures, was found to be quasitricritical and weakly first order. This implies that the smectic-A-smectic-C transition in the racemate locates at a special point where four critical lines intersect.     

Catalytic enantioselective aldol reaction to ketones

An enantioselective aldol reaction between ketones and ketene silyl acetals is described using CuF-chiral phosphine as a catalyst. The key for high enantioselectivity was the development of a novel ligand derived from Taniaphos combined with the unique accelerative effect of PhBF3K. These conditions are applicable to various substrates such as aromatic, aliphatic, and heteroaromatic ketones. In the case of substituted nucleophiles, the reaction proceeds well. The diastereoselectivity is independent of ketene silyl acetal geometry. This is the first example of a catalytic enantio- and diastereoselective aldol reaction to ketones using ketene silyl acetals.