A triflic imide (Tf(2)NH) catalyzed isomerization of kinetically favourable silyl enol ethers into thermodynamically stable ones was developed. We also demonstrated a one-pot catalytic reaction consisting of (2 + 2) cycloaddition and isomerization. In the reaction sequence, Tf(2)NH catalyzes both of the reactions.

Direct C-H functionalization and arylation of benzyl ethers has been accomplished via photoredox organocatalysis. The productive merger of a thiol catalyst and a commercially available iridium photoredox catalyst in the presence of household light directly affords benzylic arylation products in good to excellent yield. The utility of this methodology is further demonstrated in direct arylation ...

Enantioenriched, highly functionalized cyclopropane derivatives were prepared by a simple and green approach using monosaccharide-based chiral crown ethers as phase transfer catalysts. The Michael-initiated ring closure (MIRC) reactions of diethyl bromomalonate with 2-cyano-3-phenylacrylate took place complete diastereoselectivity in the presence lariat derived from carbohydrates enantioselecti...

Recently we reported the profound effects of second-sphere crown ether binding upon the redox energetics and intervalence spectroscopy of selected mixed-valence (Crowd metal complex associatino is driven primarily by ether oxygen/ ammine hydrogen interactions, where the H-bond-donating capability of NH3 is greatly enhanced by coordination to a transition-metal cation.) For delocalized species s...

The quantitative analysis and identification of the radiolytic products of dicyclohexano-18-crown-6 (DCH18C6), 4',4''(5'')-di-tert-butyldicyclohexano-18-crown-6 (DtBuCH18C6) and benzo-18-crown-6 (B18C6) in 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide ([C4mim][NTf2]) ionic liquid after irradiation were performed for the first time. It was found that the yield for radiolytic des...

1,4-Dioxane adsorbs on Pd(111) at 80 K to form an overlayer saturating at an exposure of ~4 L (1 L=1×10−6 Torr s) and desorbs with a peak centered at ~268 K in temperature-programmed desorption. Multilayer growth commences for exposures >2 L suggesting that they form before the monolayer is completed. The multilayers desorb at ~160 K. Reflection–absorption infrared spectroscopy of both normal a...

Self-assembly, templation and biomimetics are three important, overlapping areas in supramolecular chemistry. Some contributions to these three areas are introduced. Novel substituted trispyridylmethanol derived ligands were synthesized to mimic the active site of carbonic anhydrase. The key two-step process in constructing the trispyridylmethanol core structure is proven to be more efficient t...

A chiral, crown-ether-functionalized bisurea gelator forms supramolecular gels in ionic liquids. The resulting ionogels show a remarkably high thermal stability with gel-sol transition temperatures (T(gs)) reaching more than 100 °C. The mechanical strength of these ionogels is surprisingly high and even comparable to that of cross-linked protein fibres. Furthermore, the ionogels exhibit rapid s...

The number of synthetic methods enabling the preparation of ammonium-based rotaxanes has increased very rapidly in the past ten years. The challenge in the synthesis of rotaxanes results from the rather weak interactions between the ammonium-containing rod and the crown ether macrocycle in the pseudorotaxane structure that rely mostly on O*H hydrogen bonds. Indeed, no strong base or polar solve...

The complex [NdL](III) is based upon a crown ether-appended ditopic cryptate ligand and demonstrates a near-infrared fluorescence response to Ba(II).