Novel N,N,P-tridentate ligands for the highly enantioselective copper-catalyzed 1,4-addition of dialkylzincs to enones

Use of 0.25 mol % of the N, N, P-tridentate ligand containing the 2-quinolyl moiety ( 1 and 2) and 0.1 mol % of Cu(OTf) 2 enabled the enantioselective 1,4-addition of dialkylzincs to cyclic enones to produce 1,4-adducts in up to 99% ee.     

Asymmetric anionic polymerization of maleimides bearing bulky substituents

Asymmetric anionic homopolymerizations of N‐substituted maleimide (RMI) bearing bulky substituents [R = benzyl, diphenylmethyl (DPhMI), 9‐fluorenyl (9‐FlMI), triphenylmethyl, (diphenylmethyloxycarbonyl)methyl, (9‐fluorenyloxycarbonyl)methyl] were carried out with complexes of organometal compounds (alkyllithium, diethylzinc) with six chiral ligands to obtain optically active polymers. The chiroptical properties of the polymers were affected strongly by the substituents on nitrogen in the maleimide ring, the organometal and chiral ligands. Poly(DPhMI) initiated by an n‐butyllithium/(−)‐sparteine (Sp) complex showed a positive specific rotation ([α] +60.3°). Poly(9‐FlMI) prepared with a florenyllithium/Sp complex exhibited the highest specific rotation (+65.7°). The specific rotations of the poly(RMI) obtained were attributed to different contents between the stereogenic centers (S,S) and (R,R) based on threo‐diisotactic structures of the main chain. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 310–320, 2000     

A reversible near-infrared fluorescence probe for reactive oxygen species based on Te-rhodamine

We have designed and synthesized a reversible near-infrared (NIR) fluorescence probe, 2-Me TeR, for reactive oxygen species (ROS), utilizing the redox properties of the tellurium (Te) atom. 2-Me TeR is oxidized to fluorescent 2-Me TeOR by various ROS, while the generated 2-Me TeOR is quickly reduced in the presence of glutathione to regenerate 2-Me TeR. This redox-induced reversible NIR-fluorescence response of 2-Me TeR allowed us to detect the endogenous production of ROS and subsequent homeostatic recovery of the intracellular reductive environment in hydrogen peroxide-stimulated HL-60 cells. This probe is expected to be useful for monitoring the dynamics of ROS production continuously in vivo.     

Monolayer properties of mixtures of poly(n-stearyl methacrylate), poly(n-lauryl methacrylate), and their corresponding copolymers

The monolayer properties of poly(n-stearyl methacrylate), poly(n-lauryl methacrylate), and their mixtures at various ratios of the two polymers have been studied from the measurements of their surface pressure–area isotherms at air–water interface. The monolayer properties of their mixtures have been compared with those of their corresponding copolymers. The results show that the isotherms of the mixed monolayers have two break points at higher pressures than that of poly(n-lauryl methacrylate). This suggests that the mixtures may form more stable films that consist of separate phases of the two homopolymers, although each phase may contain a small amount of the other. The isotherms of the copolymer monolayers indicate a phase transition from liquid condensed to solid film between 50 segment mole % and 70% poly(n-stearyl methacrylate). The monclayer of these copolymers has properties that differ from those of the corresponding mixtures of two pure homopolymers and is more compatible than the mixtures of pure homopolymers.     

Properties of a two-beam laser diode and focusing characteristics of a two-beam optical head

Dynamic wavelength shifts of a monolithic, two-beam laser diode for a two-beam optical head in optical disk drives were analyzed with a streak camera system. The wavelength shift did not exceed 3 nm for the recording beam which was operated in a series of pulses, and the reproducing beam which was operated continuously showed no shift. The focusing characteristics on the basis of the wavelength shift and specifications of the optical head were also calculated. The dynamic displacement of the focal points caused by the wavelength shifts was so small as compared with the depth of focus in the optical head that the recording and reproducing characteristics were hardly influenced.     

Asymmetric reactions with cyclodextrins

Cyclodextrins have great potential for exploitation as a useful tool for asymmetric induction. Many kinds of asymmetric reaction have been achieved in the presence of cyclodextrin under various conditions such as the solid phase, heterogeneous suspension or homogeneous aqueous or organic solution. Complexation is essential for asymmetric induction. What is necessary to improve CDs for greater asymmetric induction?     

Theoretical study on the polymerization mechanism of substituted maleimides by using a chiral catalyst with Zn

It is possible to synthesize poly(N-substituted maleimide) by using a chiral complex consisting of a zinc and N-diphenylmethyl-1-benzyl-2-pyrrolidinoethanamine (DPhBP). The optical specific rotations [α]₄₃₅²⁵ in obtained polymers depend on the chirality of ligands in the catalysts. In the present study, density functional theory (DFT) calculations were adopted to investigate the polymerization mechanism in detail. The bulky diphenylmethyl group in the chiral ligand is effective to enhance the formation of the product in the initiation reaction. The geometry related to the pyrrolidine ring of the chiral ligand in the Zn catalyst is responsible for determining the configuration of polymers. It was also confirmed that the bulky substituent on the N atom of the N-substituted maleimide is another factor for obtaining polymers with high [α]₄₃₅²⁵.     

22,-Dimethyl-4-phenyloxazoline and 2,2-dimethyl-4,5-diphenylimidazolidine as new chiral auxiliaries. Applications to asymmetric nitrile oxide cycloadditions

Asymmetric dipolar cycloadditions of a nitrile oxide to the acrylamide derivatives of two new chiral auxiliaries, (R)-2,2-dimethyl-4-phenyloxazolidines and (S,S)-2,2-dimethyl-4,5-diphenylimidazolidine, show satisfactorily high diastereoselectivities (up to 91%).     

Structural Effects of Oligosaccharide-Branched Cyclodextrins on the Dual Recognition toward Lectin and Drug

Bi-galactose-branched cyclodextrins (Bi-Gal-CDs)(1–6) having different spacer arm lengths between two terminal galactoses were foundto have the optimum length for association with PNA lectin. Also, the inclusioninteraction of the drug depended on the length of the spacer arms. The dual association of thesecompounds was quantitatively evaluated by SPR and compared to the other oligosaccharide-branchedCDs (Scheme 1). The number and the length of the spacer arm are important for theassociation both with the lectin and drug for the purpose of targeting drug-delivery systems.The association constants K of bi-Gal-CD (2) with rat liver cells showed a 60 timeshigher association than with PNA. Direct evidence of the association between PNA andbi-Gal-CD (2) was characterized by AFM observations. The results obtained strongly suggested a method to find a new design for the targeting drug carrier. In order toincrease the association with the cell, a sufficient spacer arm length is necessary for the effectivedual recognition of the oligosaccharide-CDs. In order to increase the inclusion of thedrug, the CD structure of a multi-saccharide branch is necessary.