Palladium-Catalyzed Regioselective C4-H Acyloxylation of Indoles with Carboxylic Acids via a Transient Directing Groups Strategy.

The development of an efficient method for the synthesis of C4 oxy-substituted indoles is an appealing yet challenging task. Herein, we report a general palladium-catalyzed TDG approach for the direct C4-H acyloxylation of indoles. The protocol features atom and step economy, excellent regioselectivity, and good tolerance of functional groups. Moreover, the reaction can accommodate a range of carboxylic acids including benzoic acids, phenylacetic acids, and aliphatic acids.

Self-assembled metallogels formed from N,N',N''-tris(4-pyridyl)trimesic amide in aqueous solution induced by Fe(III)/Fe(II) ions.

In this work, we report self-assembled metallogels formed from a ligand of trimesic amide, N,N',N''-tris(4-pyridyl)trimesic amide (TPTA), induced by Fe(III)/Fe(II) ions. TPTA is difficult to dissolve in water even in the presence of some metal ions such as Cu(2+), Co(2+), Ni(2+), K(+), Na(+) and Mg(2+) under heating, and it exhibits no gelation ability. Interestingly, upon heating TPTA can be dissolved easily in aqueous solution containing Fe(3+)/Fe(2+), and subsequently self-assembled into metallogels after cooling. The metallogels could also be formed in aqueous solutions of mixed metal ions containing Fe(3+)/Fe(2+), indicating that the other metal ions do not affect the formation of Fe(III)-TPTA and Fe(II)-TPTA metallogels. The high selectivity of metallogel formation to Fe(3+)/Fe(2+) may be used for application in the test of Fe(3+)/Fe(2+). The metallogels obtained are characterized by scanning electron microscopy, Fourier transform infrared spectra, nuclear magnetic resonance spectra, rheological measurements and scanning tunneling microscopy. The results indicate that TPTA can self-assemble into fibrous aggregates in Fe(3+)/Fe(2+) aqueous solution through the metal-ligand interactions and intermolecular hydrogen bonding. This kind of metallogel also possesses good mechanical properties and thermoreversibility.

Heat-set gels formed from easily accessible gelators of a succinamic acid derivative (SAD) and a primary alkyl amine (R-NH2).

Currently, the design and construction of an intelligent stimuli-responsive gel system is still a significant challenge. We present here a new gel system from which the formation of heat-set gels, conventional gels and irreversible heat-set gels can be achieved in aromatic solvents. This gel system is based on two-component gelators containing a succinamic acid derivative (SAD) and a primary alkyl amine (R-NH2). With the increase of temperature to 85 °C, a rarely reported reversible heat-set gel (gel formation with the increase of temperature) is afforded. Upon addition of fatty acids into two-component gelators, a conventional gel (gel formation with the decrease of temperature) is formed. When the fatty acid is replaced with dicarboxylic acid, a new heat-set gel is generated, which is irreversible and thermally super-stable. X-ray diffraction analysis reveals that the formation of a reversible heat-set gel relies on electrostatic interactions, hydrogen bonds, and hydrophobic interactions. These two-component gelators show a perfect gel system for the formation of diverse gels including heat-set gels, conventional gels and irreversible heat-set gels. The tunable strategy demonstrated in this letter may provide a new way for creation of more functional gels in gel science.

A microporous hydrogen-bonded organic framework: exceptional stability and highly selective adsorption of gas and liquid.

An extremely stable hydrogen-bonded organic framework, HOF-8, was fabricated. HOF-8 is not only thermally stable but also stable in water and common organic solvents. More interestingly, desolvated HOF-8 exhibits high CO2 adsorption as well as highly selective CO2 and C6H6 adsorption at ambient temperature.