Simultaneous catalytic removal of NOϰ and diesel soot particulates

The simultaneous removal of NO_? and soot particulates in an oxidizing atmosphere is desirable for the aftertreatment of diesel exhausts. After briefly reviewing the development of catalysts for reactions involving carbons, our recent studies on the simultaneous NO_?–soot removal using perovskite-related and spinel-type oxides are described.     

Electrochiroptical systems based on biphenyl-2,2′-diyl-type dicationic dyes: strong chiroptical signals through the transmission of point chirality to axial chirality

Huge CD amplitude (A = +538) was attained by diastereomeric preference (50% de) for the title dication with two bis[4-(R)-sec-butoxyphenyl]methylium units in benzene at 23 °C. Intramolecular π-π stacking is the origin for effective transmission of point chirality to axial chirality to attain the chiroptical enhancement of 400-times. Thanks to the strong CD signaling, chiroptical changes upon electrolysis could be readily detected, thus realizing a new class of electrochiroptical response systems. Chiroptical properties could also be modified by solvent polarity.     

The mechanism of photocatalytic hydrogen production from gaseous methanol and water: IR spectroscopic approach

IR spectroscopic and volumetric study under reaction conditions of the mechanism of photocatalytic hydrogen production from gaseous methanol and water revealed that CO₂ and H₂ were produced by reaction between adsorbed CH₃O(ad) and H₂O. Another reaction path for H₂ production, CH₃ OH(ad) → H₂ + HCHO, was suggested which is dominant in the absence of water.     

Three-way-output response system by electric potential: UV-vis, CD, and fluorescence spectral changes upon electrolysis of the chiral ester of tetracyanoanthraquinodimethane

The newly prepared tetracyanoanthraquinodimethane (TCNAQ) derivatives 1a,b with a chiral auxiliary are good electron acceptors and exhibit weak circular dichroism (CD) based on the absorption of TCNAQ. The twin-type electron acceptor 1c with two TCNAQ units shows larger ellipticity by exciton coupling. UV-vis, CD, and fluorescence spectra were changed drastically upon electrochemical reduction of 1c, which demonstrates the unprecedented three-way-output response system.     

Spin-lattice relaxation time as a useful indicator for the 13CNMR assignment of terminal cis- and trans-methyls in 2-methyl-1-propenyl moiety

T₁ gives a clue to assign cis- and trans-methyl carbons in 2-methyl-1-propenyl moiety.     

Multi‐input–Multi‐output Molecular Response System Based on Dynamic Redox Behavior of Hexaphenylethane‐type Electron Donors with the Tetrahydrophenanthrazepine Skeleton: Strong Chiroptical Signals through the Transmission of Point Chirality to Helicity

The title heterocyclic donors undergo reversible C? C bond formation/cleavage upon electron transfer (dynamic redox behavior). The helical sense in both neutral and cationic states is interconvertible by facile ring flipping. The π‐type asymmetric center on the azepine nitrogen atom induces a significant degree of diasteromeric preference, thus endowing strong CD activity based on exciton coupling. Chiroptical properties could be modified not only by redox reactions but also by heat and protonation. The present redox pairs can serve as unprecedented three‐way‐input (e, H⁺, Δ) and two‐way‐output (UV/Vis, CD) response systems.     

Enantioselective Strecker-type reaction to sulfonylimines having a 2-pyridylsulfonyl group as a novel stereocontroller

A catalytic enantioselective Strecker-type reaction to N-(2-pyridylsulfonyl)imines in the presence of chiral bis(oxazoline)s afforded the products with a high enantioselectivity. A dynamically induced new chiral center on the sulfur by discriminative coordination of a chiral Lewis acid to one of the sulfonyl oxygens efficiently controlled the enantioselectivity.     

Asymmetric 1,4-addition of alkenylzirconium reagents to α,β-unsaturated ketones catalyzed by chiral rhodium complexes

Highly enantioselective 1,4-addition of alkenylzirconocene chlorides to α,β-enones was found to be catalyzed by a chiral rhodium complex generated from [Rh(cod)(MeCN)₂]BF₄ and (S)-BINAP. The reaction can be applied to either cyclic or acyclic enones and the optical yield was up to 99% ee. The reaction mechanism would involve the transmetalation between the alkenylzirconocene chloride and the rhodium complex to give the alkenylrhodium species as a key intermediate.