Ab initio molecular orbital study on three feasible mechanisms for substitution of the vinylic carbon in F2C=C(OMs)BMe3−

A substitution on 2,2-difluorovinylic carbon was investigated by using ab initio molecular orbital calculations. Three feasible mechanisms, which are the S_N1-like, the S_N2-type and the addition-elimination mechanisms, were ex- amined for a model borate, 2,2-difluoro-1-mesyloxyvinyl(trimethyl)borate. Four TSs were obtained depending on the position of Li⁺ around the vinylborate although activation energies in the gas phase are rather high (ca. 30–40 kcal mol⁻¹) in comparison with that expected from the experimental conditions. It was confirmed at the SCRF-IPCM calculations that the solvent effect reduces the acti- vation energy of one S_N2-type mechanism very much (4. l kcal mol⁻¹ at the B3LYP/6-31+G^*//RHF/6-31+G^/s* level of theory) while those for the other mechanisms do not change very much. Therefore, the S_N2-type mechanism is applicable to the substitution reaction observed for the vinylborate.     

Trichlorosilyl triflate for enantioselective direct-type aldol reaction with chiral phosphine oxide

Trichlorosilyl triflate, in the presence of a chiral Lewis base catalyst, provides an effective method for the enantioselective direct-type aldol reaction of aldehydes and ketones. A chiral Lewis base induces both the production and activation of trichlorosilyl enol ether, yielding an aldol product in good yield and with high diastereo- and enantioselectivities.     

Highly bent crystals formed by restrained π-stacked columns connected via alkylene linkers with variable conformations

A reproducible formation of strongly bent crystals was accomplished by structurally restraining macrocyclic π-conjugated molecules. The model π-units consist of two 9,10-bis(2-thienylethynyl)anthracenes with a strong propensity for stacking, which are connected in a macrocyclic fashion via two alkylene linkers. The correlation between the crystalline morphology and the macrocyclic structures restrained by a variety of flexible alkylene linker combinations was systematically studied. Bent crystals were obtained only with specific alkylene linkers of appropriate chain length. The alkylene linkers can adopt different conformations in the crystal packing, so as to fill voids within the macrocycle. The ability to form several similar molecular structures with different alkylene conformations gives rise to contaminations of different crystalline phases within a single crystal, and it is these phase contaminations which are responsible for the bending of the crystals.     

Halichonadins G-J, new sesquiterpenoids from a sponge Halichondria sp.

Three new dimeric sesquiterpenoids, halichonadins G-I (1-3), and one new eudesmane sesquiterpenoid possessing a 1-phenethyl urea moiety, halichonadin J (4), were isolated from a marine sponge Halichondria sp. Halichonadins G (1) and H (2) are homo-dimers of eudesmane sesquiterpenoid, linked through a methyl 2-{1-(2-amino-2-oxoethyl)ureido}acetate fragment and a 2-hydroxymalonamide fragment, respectively, while halichonadin I (3) is a new hetero-dimer of eudesmane sesquiterpenoid linked through a urea fragment. The structures of 1-4 were elucidated on the basis of spectroscopic data.     

Soft-sputtering of insulin films in argon-cluster secondary ion mass spectrometry

In secondary ion mass spectrometry (SIMS) of organic substances, the dissociation of the sample molecules is crucial. We have developed SIMS equipment capable of bombardment, where the primary ions are argon cluster ions with kinetic energy per atom controllable down to 1 eV. We previously reported the detection of intact ions of insulin and cytochrome C using this equipment. In this paper, we present a detailed characterization of the emission of secondary ions from insulin, focusing on the difference in secondary ion yield between intact ions and fragment ions by varying the incident angle of the cluster ions. The emission intensity of the intact ions was changed drastically due to the exposed dosage and incident angle of the cluster ions in contrast to the fragment ions. We discuss these results based on the manner in which the argon-cluster ions collide with the organic solid.     

Efficient and stereoselective synthesis of the disaccharide fragment of incednine

Efficient and stereoselective synthesis of a disaccharide fragment, 2-deoxy-4-O-(N'-monodemethyl-D-forosaminyl)-2-methylamino-β-D-xylopyranoside, of a novel antibiotic, incednine (1), is described. The key β-stereoselective formation of a 2,3,4,6-tetradeoxy-4-methylamino glycoside bond was achieved by remote participation-assisted glycosylation.     

The room-temperature synthesis of anisotropic CdHgTe quantum dot alloys: a "molecular welding" effect

The room-temperature chemical transformation of spherical CdTe nanoparticles into anisotropic alloyed CdHgTe particles using mercury bromide in a toluene/methanol system at room temperature has been investigated. The resulting materials readily dissolved in toluene and exhibited a significant red-shift in the optical properties toward the infrared region. Structural transformations were observed, with electron microscopy showing that the CdTe nanoparticles were chemically attached ('welded') to other CdTe nanoparticles, creating highly complex anisotropic heterostructures which also incorporated mercury.     

Expanded porphyrins and aromaticity

meso-Aryl-substituted expanded porphyrins that are porphyrin homologues consisting of more than five pyrrolic units are a nice platform to realize diverse aromatic and antiaromatic species as well as stable radical species. They are also an ideal series to realize topologically twisted molecules with distinct M?bius aromaticity and antiaromaticity.