Rhenium-Catalyzed Cyclization via 1,2-Iodine and 1,5-Hydrogen Migration for the Synthesis of 2-Iodo-1H-indenes

A rhenium complex catalyzed the formation of 2-iodo-1H-indene derivatives through iodine and hydrogen migration of 3-iodopropargyl ethers. The reaction proceeded via generation of 1-iodoalkenylrhenium carbene species by sequential 1,2-iodine and 1,5-hydrogen shifts with readily available precursors under neutral conditions. The reaction mechanism and the reactivity of the generated alkenylcarbene species were also investigated

Amine-Promoted anti-Markovnikov Addition of 1,3-Dicarbonyl Compounds with Terminal Alkynes under Rhenium Catalysis

Amines have been identified to greatly accelerate the intermolecular anti-Markovnikov addition of carbon nucleophiles to unactivated terminal alkynes. Using a combination of [ReBr(CO)3(thf)]2 and iPr2NEt, construction of cyclic all-carbon quaternary centers was achieved with various 1,3-ketoesters, diketones, and diesters with lower catalyst loading under milder conditions. The type of addition could be easily controlled by choice of additive, highlighting the unique features of rhenium catalysi

Mechanistic Insights into Rhenium-Catalyzed Regioselective C-Alkenylation of Phenols with Internal Alkynes

A (μ-aryloxo)rhenium complex was isolated and confirmed as a key precatalyst for rhenium-catalyzed ortho-alkenylation (C-alkenylation) of unprotected phenols with alkynes. The reaction exclusively provided ortho-alkenylphenols; the formation of para or multiply alkenylated phenols and hydrophenoxylation (O-alkenylation) products was not observed. Several mechanistic experiments excluded a classical Friedel-Crafts-type mechanism, leading to the proposed phenolic hydroxyl group assisted electrophilic alkenylation as the most plausible reaction mechanism. For this purpose, the use of rhenium, a metal between the early and late transition metals in the periodic table, was key for the activation of both the soft carbon-carbon triple bond of the alkyne and the hard oxygen atom of the phenol, at the same time. ortho-Selective alkenylation with allenes also provided the corresponding adducts with a substitution pattern different from that obtained by the addition reaction with alkynes

Rhenium-Catalyzed Regioselective ortho-Alkenylation and [3 + 2 + 1] Cycloaddition of Phenols with Internal Alkynes

An operationally simple and direct rhenium-catalyzed ortho-alkenylation (C-alkenylation) of unprotected phenols with alkynes was developed. The protocol provided ortho-alkenylphenols exclusively, and formation of para- or multiply alkenylated phenols and hydrophenoxylation (O-alkenylation) products were not observed. The [3 + 2 + 1] cycloaddition of phenols and two alkynes via ortho-alkenylation was also demonstrated, in which the alkynes functioned as both two- and one-carbon units. These reactions proceeded with readily available starting materials under neutral conditions without additional ligands

Chromium-Mediated Stannylcyclopropanation of Alkenes with (Diiodomethyl)stannanes

A stannyl-group-substituted gem-dichromiomethane species, generated in situ from CrCl2, TMEDA, and tributyl(diiodomethyl)stannane, worked as an efficient stannylcarbene equivalent to promote cyclopropanation of alkenes. The reaction provided synthetically useful stannylcyclopropanes directly from commercially available unactivated alkenes without using potentially flammable alkylzinc and diazo compounds. Structural characterization of stannyl- and germyl-group-substituted gem-dichromiomethane complexes and the effect of group 14 elements containing substituents for cyclopropanation are also described

Modulating the Properties of Azulene‐Containing Polymers through Controlled Incorporation of Regioisomers

Two libraries of random conjugated polymers are presented that incorporate varying ratios of regioisomeric azulene units connected via the 5‐membered or 7‐membered ring in combination with bithiophene or fluorene comonomers. It is demonstrated that the optoelectronic and stimuli‐responsive properties of the materials can be systematically modulated by tuning the relative percentage of each azulene building block in the polymer backbone. Significantly, these materials exhibit stimuli‐responsive behavior in the solid state with spin‐coated thin films undergoing rapid and reversible color switching. Ultimately, this work introduces a new design strategy in which the optoelectronic properties of conjugated polymers can be modulated by varying only the regiochemistry of the constituent building blocks along a polymer chain

Synthesis and Properties of Sila[n]helicenes via Dehydrogenative Silylation of C-H Bonds under Rhodium Catalysis

Use of a rhodium catalyst with (R)-(S)-BPPFA ligand allows efficient synthesis of sila[n]helicenes via dehydrogenative silylation of C-H bonds. By selecting the proper ligands, the current method provides the ability to prepare unsymmetrical sila[n]helicene derivatives without any oxidants. The resulting sila[6]helicene is a rare example of a five-membered ring-fused [6]helicene, which was isolated as a single pure enantiomer without substituents on the terminal benzene rings

Thermophysical Properties Measurement of High-Temperature Liquids Under Microgravity Conditions in Controlled Atmospheric Conditions

Microgravity conditions have advantages of measurement of surface tension and viscosity of metallic liquids by the oscillating drop method with an electromagnetic levitation (EML) device. Thus, we are preparing the experiments of thermophysical properties measurements using the Materials-Science Laboratories ElectroMagnetic-Levitator (MSL-EML) facilities in the international Space station (ISS). Recently, it has been identified that dependence of surface tension on oxygen partial pressure (Po2) must be considered for industrial application of surface tension values. Effect of Po2 on surface tension would apparently change viscosity from the damping oscillation model. Therefore, surface tension and viscosity must be measured simultaneously in the same atmospheric conditions. Moreover, effect of the electromagnetic force (EMF) on the surface oscillations must be clarified to obtain the ideal surface oscillation because the EMF works as the external force on the oscillating liquid droplets, so extensive EMF makes apparently the viscosity values large. In our group, using the parabolic flight levitation experimental facilities (PFLEX) the effect of Po2 and external EMF on surface oscillation of levitated liquid droplets was systematically investigated for the precise measurements of surface tension and viscosity of high temperature liquids for future ISS experiments. We performed the observation of surface oscillations of levitated liquid alloys using PFLEX on board flight experiments by Gulfstream II (G-II) airplane operated by DAS. These observations were performed under the controlled Po2 and also under the suitable EMF conditions. In these experiments, we obtained the density, the viscosity and the surface tension values of liquid Cu. From these results, we discuss about as same as reported data, and also obtained the difference of surface oscillations with the change of the EMF conditions