Stereoselective synthesis of scyphostatin hydrophilic moiety

A stereoselective synthesis of scyphostatin hydrophilic moiety was accomplished. Substrate- and reagent-controlled dihydroxylation of tri- and monosubstituted alkenes afforded desired diols, respectively. Chemo- and stereoselective allylation of α-(methoxycarbonyl)cyclohexanone provided allylcyclohexanol. Oxidative cleavage of glycol and subsequent β-elimination of siloxycyclohexanone furnished the desired epoxycyclohexenone.     

Rate-accelerating effect by the neighboring-group participation of protecting groups in the dehydrative cyclization of 1,3,5-triketones

Neighboring-group participation of an acyl protecting group efficiently promotes the Br?nsted acid-catalyzed dehydrative cyclization of 1,3,5-triketones to gamma-pyrones, whereas a bulky silyloxy group in the beta-position retards the cyclization. This reaction provides an efficient synthetic route for a common intermediate for the synthesis of gamma-pyrone-containing bioactive natural products.     

Catalytic enantioselective organozinc addition toward optically active tertiary alcohol synthesis

A highly enantioselective organozinc (R₂Zn) addition to a series of aldehydes and ketones was developed based on conjugate Lewis acid–Lewis base catalysis. Optically active secondary and tertiary alcohols were obtained in high yields with high enantioselectivities without Ti(IV) compounds. Bifunctional chiral 3,3′‐diphosphoryl‐BINOL ligands were designed and prepared through a phospho‐Fries rearrangement as a key step. On the other hand, bifunctional chiral phosphoramide ligands were designed and prepared from L ‐valine. Mechanistic studies were performed by X‐ray analyses of Zn(II) cluster and chiral ligands, a ³¹P NMR experiment on Zn(II) complexes, and stoichiometric reactions with some chiral or achiral Zn(II) complexes to propose a transition state assembly that includes monomeric active intermediates. © 2008 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 8: 143–155; 2008: Published online in Wiley InterScience ( www.interscience.wiley.com ) DOI 10.1002/tcr.20146     

Efficient free energy calculation of water across lipid membranes

An efficient free energy (FE) calculation of a water molecule to go across lipid membranes is presented. Both overlapping distribution and cavity insertion Widom methods are complementarily used. The former is useful for a dense region where water molecules are found, i.e., from the interfacial to bulk water region, while the latter works well in the low density region, i.e., the hydrocarbon region. Since both methods evaluate the excess chemical potential of water, the obtained FE profile is free from the fitting problem usually arisen when a FE difference method is used. A diphytanyl phosphatidylcholine bilayer is used for our test calculations. An excellent and fast convergence of the chemical potential is obtained when each method is applied for the appropriate region. The estimated FE barrier using the Ewald method for the electrostatic interaction is approximately 7.2 kcal/mol, which is higher than that using the interaction cutoff of 20 A by about 0.9 kcal/mol.     

Asymmetric intramolecular Cannizzaro reaction of anhydrous phenylglyoxal

The use of anhydrous phenylglyoxal provides a solution to the problem of low reactivity in the asymmetric intramolecular Cannizzaro reaction with alcohols. Double asymmetric induction was achieved in the reaction of anhydrous phenylglyoxal with d-(+)-menthol promoted by a (S,S)-t-BuBox·copper(II) hexafluoroantimonate complex.     

Burning velocity measurements of fluoropropanes by the spherical-vessel method

Burning velocity measurements of six types of fluoropropanes including structural isomers were carried out in order to understand the flammability of hydrofluorocarbons (HFC). The burning velocity (S_u) was determined by applying a spherical flame model to the pressure rise during combustion, which was measured at room temperature and at initial pressures of 80-107 kPa over a wide range of HFC/air concentrations. The maximum S_u of 1-fluoropropane (HFC-281fa), 2-fluoropropane (HFC-281ea), 1,3-difluoropropane (HFC-272fa), 2,2-difluoropropane (HFC-272ca), 1,2,3-trifluoropropane (HFC-263ea), and 1,1,1-trifluoropropane (HFC-263fb) was 35.0, 31.8, 31.9, 21.2, 25.7, and 14.5 cm s⁻¹, respectively. Note that the maximum S_u of HFC-263ea was appreciably higher than that of HFC-272ca, which shows the importance of the F-atom distribution, as well as of the F/H ratio in the HFC molecule. The results of equilibrium calculation for these HFCs showed that S_u is positively correlated with the flame temperature and the concentrations of the active chain carriers H and OH in the flame. We conducted a trial to interpret the magnitude of S_u by means of the effects of substituents for C₁-C₃ HFCs. As a result, it has been found that the order of inhibition efficiency for S_u decreases in the order of CF₃ > CF₂ > CF.