Synthetic studies toward maytansinoids (2) a new strategy based on asymmetric induction by heteroconjugate addition of methyllithium onto pyranosyl hetero-olefins

The functionalized pyranosyl hetero-olefins $\text{4a}$, $\text{13}$ and $\text{15}$ received a remarkable diastereoselective addition of methyllithium to form $\text{threo}$ adducts, one of which was introduced into a possible synthetic intermediate as $\text{3}$ for maytansine ($\text{1}$) along Scheme I.     

Chloroprene as a source of fine chemicals: palladium-catalyzed synthesis of terminal allenes

[reaction: see text] Several functionalized terminal allenes were prepared in moderate to excellent yield by a palladium-catalyzed reaction of chloroprene (2-chloro-1,3-butadiene) with soft nucleophiles.     

On the Theory of Gravitational Field in Finsler Spaces

Some structural considerations are made on the Finslerian gravitational field: A Finslerian metrical structure such as g_λχ(x, y) = γ_λχ(x) + h_λχ(x, y) is proposed, where γ_λχ denotes the Riemann metric of Einstein's gravitational field, while hλχ the Finsler metric induced by the Riemann metric h_ij(y) of the internal field; The intrinsic behaviour of the internal variable y, which is expressed as ?ⁱ = K(x, y) y^j in the internal field, is grasped by the Finslerian parallelism δyⁱ (=0), which is reflected in the spatial structure of the external gravitational field by the mapping relation δy^χ = e(x) δyⁱ. The whole metrical Finsler connection D for g_λχ(i.e., Dg_λχ = 0) is determined by taking account of the intrinsic behaviour δy^χ.     

Study of a high-dimensional chaotic attractor

The nature of a very high-dimensional chaotic attractor in an infinite-dimensional phase space is examined for the purpose of studying the relationships between the physical processes occurring in the real space and the characteristics of high-dimensional attractor in the phase space. We introduce two complementary bases from which the attractor is observed, one the Lyapunov basis composed of the Lyapunov vectors and the another the Fourier basis composed of the Fourier modes. We introduce the exterior subspaces on the basis of the Lyapunov vectors and observe the chaotic motion projected onto these exteriors. It is shown that a certain statistical property of the projected motion changes markedly as the exterior subspace goes out of the attractor. The origin of such a phenomenon is attributed to more fundamental features of our attractor, which become manifest when the attractor is observed from the Lyapunov basis. A counterpart of the phenomenon can be observed also on the Fourier basis because there is a statistical one-to-one correspondence between the Lyapunov vectors and the Fourier modes. In particular, a statistical property of the high-pass filtered time series reflects clearly the difference between the interior and the exterior of the attractor.     

Novel synthesis of macrocycles with 1,1′-binaphthalene-2,2′-diol using intramolecular oxidative coupling

A new series of BINOL-based macrocycles with two phenolic protons have been synthesized via oxidative coupling reaction using CuCl(OH)-TMEDA.     

Gelation in free-radical terpolymerization of poly(allyl methacrylate) crosslinked polymer nanosphere with allyl benzoate and vinyl benzoate

Microgel-like poly(allyl methacrylate) (PAMA nanosphere) was prepared by the emulsion polymerization of AMA as the reactive crosslinked polymer nanosphere with abundant pendant allyl groups. The terpolymerization of PAMA nanosphere with allyl benzoate (ABz) and vinyl benzoate (VBz) was conducted in bulk using benzoyl peroxide as initiator at 80 °C. The gelation depended on the feed ABz/VBz molar ratio since the molecular weights of resulting poly(ABz-co-VBz)s that act as the bridges increased with an increase in the mole fraction of VBz in the feed monomer. Beyond the gel point, the sol was rapidly incorporated into the gel and the increasing tendency of the gel fraction became steeper from 70 to 95 mol% of VBz as a reflection of increased chain length of bridge between PAMA nanospheres. Moreover, the swelling ratio became lower with increasing the mole percentage of VBz in the feed monomer. These results would support the preferential incorporation of PAMA nanosphere into the gel and the longer bridge can capture more nanospheres to give a much shrunken gel.     

Fluorometric sensing of alkaline Earth metal cations by new lariat ethers having plural pyrenylmethyl groups on the electron-donating sidearms

[structure: see text] New fluorescent compounds (1), lariat ethers having plural pyrenylmethyl groups on the sidearms, were prepared, and their complexation behavior with alkaline earth metal cations was examined by fluorescence spectrometry. The pyrene excimer emission decreased accompanied with an increase in the monomer emission upon complexation with the metal ion. This finding is ascribed to the cooperative participation of one of the two sidearms in the complexation of the crown ring with the metal ion.     

PICOSECOND LASER PHOTOLYSIS STUDIES OF FLUORESCENCE QUENCHING MECHANISMS OF FLAVIN: A DIRECT OBSERVATION OF INDOLE-FLAVIN SINGLET CHARGE TRANSFER STATE FORMATION IN SOLUTIONS and FLAVOENZYMES

Formation of singlet charge transfer (heteroexcimer) states in the course of the fluorescence quenching of lumiflavin and riboflavin tetrabutyrate by indole and N-methylindole have been directly observed by means of time-resolved absorption spectral measurements using a picosecond laser photolysis method. Similar transient spectra have been observed also in the case of a flavoenzyme, D-amino acid oxidase.