Jaehoon Choe

Synthesis of symmetrical and unsymmetrical diarylalkynes from propiolic acid using palladium-catalyzed decarboxylative coupling.

Symmetrical diarylalkynes were obtained from propiolic acid (or 2-butynedioic acid) and aryl halides in good yields. The optimized reaction conditions were 2.0 equiv of aryl halide, 1.0 equiv of propiolic acid, 5.0 mol % Pd(PPh(3))(2)Cl(2), 10.0 mol % 1,4-bis(diphenylphosphino)butane (dppb), 2.0 equiv of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and dimethyl sulfoxide (DMSO) as the solvent. The coupling reaction of 2-butynedioic acid with aryl halides required 110 °C. The coupling reaction showed tolerance for functional groups such as ester, ketone, and aldehyde and exhibited chemoselectivity. In the coupling reaction of propiolic acid with aryl bromide, the diarylated product was the major one at 80 °C, even though 1 equiv of aryl halides was employed. However, among the monoarylated products that were formed predominantly at 25 and 50 °C in the coupling reaction with aryl iodide, more Sonogashira coupling product was obtained than the decarboxylative coupling product. Unsymmetrical diarylalkynes were also synthesized via this method, in which all reagents, including propiolic acid, aryl iodide, and aryl bromides were added at the beginning of the reaction.

The scope and limitation of nickel-catalyzed aminocarbonylation of aryl bromides from formamide derivatives.

Nickel-catalyzed aminocarbonylation of aryl halides is described. A well-defined air-stable nickel-phosphite catalytic system (Ni(OAc)(2).4H(2)O/phosphite 1) effectively promoted the aminocarbonylation of aryl bromides with a range of formamides to give the corresponding aryl amide products in moderate to good yields. The less hindered formamide required lower catalytic loading for full conversion and produced higher yields than the more hindered one. It also exhibited base-dependent activity toward formamides.

Fabrication of Microcapsules for Dye-Doped Polymer-Dispersed Liquid Crystal-Based Smart Windows

A dye-doped polymer-dispersed liquid crystal (PDLC) is an attractive material for application in smart windows. Smart windows using a PDLC can be operated simply and have a high contrast ratio compared to those of other devices that employed photochromic or thermochromic material. However, in conventional dye-doped PDLC methods, dye contamination can cause problems and has a limited degree of commercialization of electric smart windows. Here, we report on an approach to resolve dye-related problems by encapsulating the dye in monodispersed capsules. By encapsulation, a fabricated dye-doped PDLC had a contrast ratio of >120 at 600 nm. This fabrication method of encapsulating the dye in a core-shell structured microcapsule in a dye-doped PDLC device provides a practical platform for dye-doped PDLC-based smart windows.

Micromixer as a Continuous Flow Reactor for the Synthesis of a Pharmaceutical Intermediate

A mixing device composed of a micron scale flow channel was applied as a continuous reactor to control exothermic reaction heat and to increase the product yield, in a synthesis of a pharmaceutical intermediate of quinolone antibiotics. The model reaction featured a fast reaction rate, high heat generation, and impurity formation due to a prolonged contact time between reactants and products. Using the micromixer reactor, the reaction heat was efficiently removed so that virtually no impurities were produced during the reaction. A product yield comparable to the theoretical value was achieved in a single micromixer unit. Optimum operating conditions were acquired from a statistical method by using factorial design, which was also verified by a CFD calculation.

Alternating magnetic field mediated micro reaction system for palladium-catalyzed coupling reactions

A continuous flow reaction system in which a palladium magnetic catalyst was immobilized and vibrated by an alternating induced magnetic field was developed. The alternating electromagnetic field improved the mixing efficiency and catalytic activity for the palladium-catalyzed coupling reactions. This flow reaction system showed good product yields for various reactions such as Sonogashira, Heck, Suzuki, Stille, Hiyama and decarboxylative coupling reactions.