Visualization of the Orientation of Amphipathic Peptides at the Air-Water Interface by X-Ray Reflectometry.

X-ray reflectivity measurements were performed for the leucine and lysine-based LKα14 peptide designed to adopt an α-helical conformation at the air-water interface. The electron density profiles along the surface normal were calculated from the atomic coordinates predicted by an electronic structure program to fit the X-ray reflectivity curve. At the concentration of the monolayer formation, the long axis of the α-helix adsorbed parallel to the water surface, and the central part was revealed to be submerged in water. On the other hand, at 100 times higher than the surface area density of the monolayer formation, the double layer is formed in which the long axis of the α-helix is parallel to the water surface and only the peptide in the second layer is submerged in water.

Kinetic resolution of racemic alpha-arylalkanoic acids with achiral alcohols via the asymmetric esterification using carboxylic anhydrides and acyl-transfer catalysts.

A variety of optically active carboxylic esters are produced by the kinetic resolution of racemic alpha-substituted carboxylic acids using achiral alcohols, aromatic or aliphatic carboxylic anhydrides, and chiral acyl-transfer catalysts. The combination of 4-methoxybenzoic anhydride (PMBA) or pivalic anhydride with the modified benzotetramisole-type catalyst ((S)-beta-Np-BTM) is the most effective for promotion of the enantioselective coupling reaction between racemic carboxylic acids and a novel nucleophile, bis(alpha-naphthyl)methanol, to give the corresponding esters with high ee's. This protocol was successfully applied to the production of nonracemic nonsteroidal anti-inflammatory drugs from racemic compounds utilizing the transacylation process to generate the mixed anhydrides from the acid components with the suitable carboxylic anhydrides.

Asymmetric cyclopropanation of 2,5-dimethyl-2,4-hexadiene by copper catalysts bearing new bisoxazoline ligands.

Some new bisoxazoline ligands with an aryl group at the 4-position and gem-dimethyl groups at the 5-position on the oxazoline ring were prepared from arylglycines. Remarkable enhancement of the trans-selectivity (trans/cis = 87/13) and the enantioselectivity (96% ee for the trans product) was demonstrated for the asymmetric cyclopropanation of 2,5-dimethyl-2,4-hexadiene with tert-butyl diazoacetate catalyzed by the new copper-bisoxazoline complex.

Reaction pathway and stereoselectivity of asymmetric synthesis of chrysanthemate with the aratani C1-symmetric salicylaldimine-copper catalyst.

The reaction pathway and the mechanism of asymmetric induction in the synthesis of (+)-trans-(1R,3R)-chrysanthemic acid methyl ester from methyl diazoacetate and 2,5-dimethyl-2,4-hexadiene in the presence of a C(1)-chiral salicylaldimine Cu(I) complex has been probed with the aid of hybrid density functional calculations. The key finding is that the alkoxycarbonyl carbene complex intermediate is intrinsically chiral and that the intramolecular hydrogen bonding in the carbene complex transmits the chirality information from the side chain to the carbene complex. Molecular orbital backgrounds of the structure of the carbene complex and the transition state of the cyclopropanation have been elucidated.