Dataset Information

A Change from Kinetic to Thermodynamic Control Enables trans-Selective Stereochemical Editing of Vicinal Diols.

ABSTRACT: Here, we report the selective, catalytic isomerization of cis-1,2-diols to trans-diequatorial-1,2-diols. The method employs triphenylsilanethiol (Ph₃SiSH) as a catalyst and proceeds under mild conditions in the presence of a photoredox catalyst and under blue light irradiation. The method is highly chemoselective, broadly functional group tolerant and provides concise access to trans-diol products which are not readily obtained using other methods. Mechanistic studies reveal that isomerization proceeds through a reversible hydrogen atom transfer pathway mediated by the silanethiol catalyst.

SUBMITTER: Zhang YA

PROVIDER: S-EPMC9373033 | biostudies-literature | 2022 Jan

REPOSITORIES: biostudies-literature

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A Change from Kinetic to Thermodynamic Control Enables trans-Selective Stereochemical Editing of Vicinal Diols.

Zhang Yu-An YA Gu Xin X Wendlandt Alison E AE

Journal of the American Chemical Society 20211220 1

Here, we report the selective, catalytic isomerization of cis-1,2-diols to trans-diequatorial-1,2-diols. The method employs triphenylsilanethiol (Ph3SiSH) as a catalyst and proceeds under mild conditions in the presence of a photoredox catalyst and under blue light irradiation. The method is highly chemoselective, broadly functional group tolerant and provides concise access to trans-diol products which are not readily obtained using other methods. Mechanistic stu ...[more]

PMID: 34928134

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Project description:Herein, a novel imprinted solid-phase extraction cartridge was fabricated to investigate the kinetic, thermodynamic, and isothermal parameters for the selective adsorption of Bisphenol A (BPA). The imprinted polymeric cartridges (BMC) for the BPA adsorption were fabricated in the presence of a template and functional monomer using the in situ polymerization technique. To prove the efficiency and selectivity of BMC, the nonimprinted polymeric cartridges (BNC) and the empty polymeric cartridges (EC) were also fabricated with and without functional monomer using the same manner for the preparation of BMC. The characterization of cartridges was performed by elemental analysis, Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET) surface area measurements, and swelling tests. BPA removal studies were performed by analyzing some parameters such as temperature, BPA concentration, flow rate, salt type, and concentration. The highest capacity was determined as 103.2 mg BPA/g polymer for a 0.75 mL/min flow rate of 0.75 M (NH4)2SO4 containing 200 mg/L BPA solution at 50 °C. NaOH (1.0 M) was used as a desorption agent. The reusability performance was examined by performing 10 consecutive cycles. The solid-phase extraction (SPE) performance was also checked to determine the enrichment and extraction recovery factors for tap water and synthetic wastewater samples. Temkin, Langmuir, Freundlich, and Dubinin-Radushkevich isotherm models were applied to BPA adsorption data examining the adsorption mechanism, surface properties, and adsorption degree. The most suitable isotherm model for BPA adsorption was determined as the Langmuir isotherm model. The thermodynamic parameters (ΔG°, ΔH°, and ΔS°) were investigated to reveal the thermodynamics of adsorption. Adsorption thermodynamic parameters (ΔH°, ΔS°, and ΔG°) were calculated using the thermodynamic equilibrium constant (thermodynamic equilibrium constant, K°) values that change with temperature. It was determined that BPA adsorption was spontaneous (ΔG° < 0) and endothermic (ΔH° > 0) and entropy increased (ΔS° > 0) at the temperatures studied in the BPA adsorption process. The rate control step in the adsorption process was examined by applying pseudo-first-order and pseudo-second-order kinetic models to the adsorption data for the investigations of BPA adsorption kinetics, and the pseudo-second-order kinetic model was found to be more suitable for describing BPA adsorption kinetics. In examining the selectivity of cartridges, structural analogues of hydroquinone, phenol, β-estradiol, and 8-hydroxyquinoline were tested.

Dataset Information

A Change from Kinetic to Thermodynamic Control Enables trans-Selective Stereochemical Editing of Vicinal Diols.

Publications

A Change from Kinetic to Thermodynamic Control Enables <i>trans-</i>Selective Stereochemical Editing of Vicinal Diols.

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