Control of viscoelasticity using redox reaction

The viscoelasticity of a fluid was tuned with the Faradaic reaction of (11-ferrocenylundecyl)trimethylammonium bromide (FTMA), a "redox-switchable" surfactant. An aqueous solution of the reduced form of FTMA exhibited a remarkable viscoelasticity in the presence of sodium salicylate (NaSal) because of the formation of three-dimensional entanglement of wormlike micelles. Electrolytic oxidation of FTMA caused the viscosity of the system to dramatically decrease and the elasticity to disappear. This drastic decrease in viscoelasticity arose from the disruption of wormlike micelles. This novel electrorheological phenomenon is expected to be applicable to ink for inkjet printers, the electrochemically controlled release of substances entrapped in wormlike micelles of FTMA, and fluid flow rate control using electric signals.     

Five new nortropane alkaloids and six new amino acids from the fruit of Morus alba LINNE growing in Turkey

Investigation of the constituents of the fruits of Morus alba LINNE (Moraceae) afforded five new nortropane alkaloids (1-5) along with nor-psi-tropine (6) and six new amino acids, morusimic acids A-F (7-12). The structures of the new compounds were determined to be 2alpha,3beta-dihydroxynortropane (1), 2beta,3beta-dihydroxynortropane (2), 2alpha,3beta,6exo-trihydroxynortropane (3), 2alpha,3beta,4alpha-rihydroxynortropane (4), 3beta,6exo-dihydroxynortropane (5), (3R)-3-hydroxy-12-[(1S,4S)-4-[(1S)-1-hydroxyethyl]-pyrrolidin-1-yll-dodecanoic acid-3-O-beta-D-glucopyranoside (7), (3R)-3-hydroxy-12-[(1S,4S)-4-[(1S)-1-hydroxyethyl]-pyrrolidin-1-yll-dodecanoic acid (8), (3R)-3-hydroxy-12-1(1R,4R,5S)-4-hydroxy-5-methyl-piperidin-1-yll-dodecanoic acid-3-O-beta-D-glucopyranoside (9), (3R)-3-hydroxy-12-[(1R,4R,5S)-4-hydroxy-5-methyl-piperidin-1-yll-dodecanoic acid (10), (3R)-3-hydroxy-12-[(1R,4R,5S)-4-hydroxy-5-hydroxymethyl-piperidin-1-yl]-dodecanoic acid-3-O-beta-D-glucopyranoside (11), and (3R)-3-hydroxy-12-[(1R,4S,5S)-4-hydroxy-5-methyl-piperidin-1-yl]-dodecanoic acid (12) on the basis of spectral and chemical data.     

Exploiting Transient Radical Cations as Brønsted Acids for Allylic C–H Heteroarylation of Enol Silyl Ethers

Intermediary radical cations, generated through single-electron oxidation of enol silyl ethers by excited Ir-based photocatalysts, can be exploited as Brønsted acids for the activation of heteroarylcyanides. This strategy enables the direct allylic C−H heteroarylation of enol silyl ethers under visible-light irradiation.     

Iridium‐Catalyzed Enantioselective C?H Alkylation of Ferrocenes with Alkenes Using Chiral Diene Ligands

The first catalytic and enantioselective C H alkylation of ferrocene derivatives with various alkenes was achieved. A cationic iridium complex, having a chiral diene ligand, and an isoquinolyl moiety as a directing group are essential for regioselective and enantioselective C H bond activation.     

Syntheses,Structures, and Reactivities of Two Chalcogen‐Stabilized Carbones

Electronic effects on the central carbon atom of carbone, generated by the replacement of the S^IV ligand of carbodisulfane (CDS) with other chalcogen ligands (Ph₂E, E=S or Se), were investigated. The carbones Ph₂E→C←SPh₂(NMe) [E=S( 1 ) or Se( 2 )] were synthesized from the corresponding salts, and their molecular structures and electronic properties were characterized. The carbone 2 is the first carbone containing selenium as the coordinated atom. DFT calculations revealed the electronic structures of 1 and 2 , which have two lone pairs of electrons at the carbon center. The trend in HOMO energy levels, estimated by cyclic voltammetry measurements, for the carbones and CDS follows the order of 2 > 1 >CDS. Analysis of a doubly protonated dication and trication complex revealed that the central carbon atom of 2 behaves as a four‐electron donor.     

Optical characterization of a nanoscale incommensurate pitch in a new liquid-crystal phase

As a remarkable orientationally ordered soft-condensed matter system, the smectic-C*(alpha) phase exhibits an incommensurate nanoscale helical pitch of more than four smectic layers. Recent theoretical advances predict the existence of a new phase showing a helical pitch of less than four smectic layers (<16 nm). By applying a novel optical technique to the study of freestanding films with increments in thickness of one smectic layer, we have measured the size of this pitch using 633 nm HeNe laser light. Our results confirm the existence of the newly predicted phase in one unique compound.     

Efficient synthesis of N-nosyl-protected 3-azabicyclo[4.3.0]nonen-8-one by an aniline- and nitrobenzene-mediated Pauson–Khand cyclization

The intramolecular Pauson–Khand cyclization in the presence of both aniline and nitrobenzene was used to improve the construction of N-nitrobenzenesulfonyl-protected 3-azabicyclo[4.3.0]nonane skeletons. We found that aniline enhanced the cyclization and that nitrobenzene prevents the concurrent reduction in this process. This combination of mediators allows for the efficient synthesis of bioactive azabicyclic nonane-type alkaloids and the use of milder deprotection conditions in the synthetic route.     

Catalytic Enantioselective Reaction of α‐Phenylthioacetonitriles with Imines Using Chiral Bis(imidazoline)–Palladium Catalysts

The catalytic enantioselective reaction of α‐phenylthioacetonitriles with imines has been developed. The reaction of various imines proceeds in good yields and diastereo‐ and enantioselectivities in the presence of chiral bis(imidazoline)–palladium catalysts. The obtained products can be converted into β‐aminonitrile or β‐aminoamide compounds without loss of enantiopurity.