Abstract Two new iodide‐containing derivatives of widely‐used Ru(II) (arene)(TosDPEN) catalysts are synthesized and evaluated in the asymmetric reduction of acetophenone under both transfer (ATH) and pressure hydrogenation (AH) conditions.
The reaction of amino acid derived N-carboxyanhydrides (NCAs) with unprotected amino acids under carefully controlled aqueous continuous flow conditions realized the formation of a range of di- and tripeptide products in 60–85% conversion at productivities of up to 535 g·L–1h–1. This required a fundamental understanding of the physicochemical aspects of the reaction resulting in the design of a custom-made continuous stirred tank reactor (CSTR) with continuous solids addition, high shear mixing, automated pH control to avoid the use of buffer, and efficient heat removal to control the reaction at 1 ± 1 °C.
A continuous-flow electrochemical synthesis platform has been developed to enable self-optimization of reaction conditions of organic electrochemical reactions using attenuated total reflection Fourier transform infrared spectroscopy (ATR FT-IR) and gas chromatography (GC) as online real-time monitoring techniques. We have overcome the challenges in using ATR FT-IR as the downstream analytical methods imposed when a large amount of hydrogen gas is produced from the counter electrode by designing two types of gas-liquid separators (GLS) for analysis of the product mixture flowing from the electrochemical reactor. In particular, we report an integrated GLS with an ATR FT-IR probe at the reactor outlet to give a facile and low-cost solution to determining the concentrations of products in gas-liquid two-phase flow. This approach provides a reliable method for quantifying low-volatile analytes, which can be problematic to be monitored by GC. Two electrochemical reactions the methoxylation of 1-formylpyrrolidine and the oxidation of 3-bromobenzyl alcohol were investigated to demonstrate that the optimal conditions can be located within the pre-defined multi-dimensional reaction parameter spaces without intervention of the operator by using the stable noisy optimization by branch and FIT (SNOBFIT) algorithm.
Abstract Despite growing applications being reported both in academia and industry, continuous flow chemistry remains a relatively untaught field across most chemistry undergraduate courses. This is particularly true in laboratory practical classes, where it is often deemed simpler to carry out synthetic reactions in traditional batch mode using round-bottomed flasks. Herein, we report the development of an undergraduate project that utilises cheap and readily available materials to construct continuous flow reactors. The students compare the performance of different types of reactors and conditions in a biphasic selective acetylation of a symmetrical diamine. Throughout the investigation, the students can vary multiple parameters as they optimise the reaction, thus actively learning and readjusting them based on their improved understanding. The experiments give the students an appreciation of continuous flow techniques in comparison to batch.
Chloramines are an important class of reagents, providing a convenient source of chlorine or electrophilic nitrogen. However, the instability of these compounds is a problem which makes their isolation and handling difficult. To overcome these hazards, a continuous-flow approach is reported which generates and immediately reacts N -chloramines directly, avoiding purification and isolation steps. 2-Chloramines were produced from the reaction of styrenes with N -alkyl- N -sulfonyl- N -chloramines, whilst N -alkyl or N,N’ -dialkyl- N -chloramines reacted with anisaldehyde in the presence of t -BuO 2 H oxidant to afford amides. Primary and secondary imines were produced under continuous conditions from the reaction of N -chloramines with base, with one example subsequently reduced under asymmetric conditions to produce a chiral amine in 94% ee.
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
2-Cyanobenzothiazoles (CBTs) are useful building blocks for: 1) luciferin derivatives for bioluminescent imaging; and 2) handles for bioorthogonal ligations. A particularly versatile CBT is 6-amino-2-cyanobenzothiazole (ACBT), which has an amine handle for straight-forward derivatisation. Here we present an economical and scalable synthesis of ACBT based on a cyanation catalysed by 1,4-diazabicyclo[2.2.2]octane (DABCO), and discuss its advantages for scale-up over previously reported routes.
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
The use of a direct arene-exchange method for the synthesis of benzyl-tethered arene/Ru/TsDPEN complexes for use in asymmetric transfer hydrogenation is reported. A series of complexes tethered through a three-carbon linear chain was also prepared. The arene-exchange approach significantly simplifies the synthetic approach to this class of catalyst and permits the ready formation of modified analogues. The approach also provides a route to racemic catalysts for use in general reductions with either hydrogen or transfer hydrogenation.
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
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