Bioorganogermanium Chemistry: Studies on C/Si/Ge Bioisosterism

Tacke, Reinhold; Heinrich, T.; Kornek, T.; Merget, Markus; Wagner, Stephan; Gross, J.; Keim, Christine; Lambrecht, Günter; Mutschler, E.; Beckerss, T.; Bernd, Michael; Reissmann, Thomas

doi:10.1080/10426509908546372

Cited by 26 publications

(8 citation statements)

References 16 publications

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“…The TMS groups were introduced in 3-cyanobromobenzene I-1a and 4-cyanobromobenzene I-1b , applying a palladium-catalyzed coupling reaction involving a phosphine ligand and hexamethyldisilane (HMDS) as the silicon source. The cyano groups were hydrolyzed under alkaline conditions, subsequently providing the key intermediates I-3a and I-3b . Intermediate I-7 was obtained from acid I-4 in three steps.…”

Section: Resultsmentioning

confidence: 99%

Design, Synthesis, and Properties of Silicon-Containing meta-Diamide Insecticides

Quan

et al. 2023

J. Agric. Food Chem.

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Silicon-containing compounds are sporadically used in crop protection and drug discovery and have demonstrated to increase the biological efficacy as well as to reduce toxicity, improve physicochemical properties, and favorably impact the environmental profile. As part of our research, we have investigated the application of bioisosteric silicon replacements in metadiamide insecticides and studied the biological activity and molecular properties of the corresponding novel compounds. At all meaningful structural elements of the meta-diamides, silicon-containing substituents were introduced and synthetic methodology was developed for their syntheses. As the most promising compound, silicon-containing meta-diamide II-18 emerged, which exhibits a very low LC 50 value of 2.00 mg/L against Mythimna separata and compares well to the reference compounds 28 (LC 50 = 0.17 mg/L) and II-20 (LC 50 = 0.27 mg/L). Our research on silicon-containing crop protection compounds once again confirmed that the biological activity can be beneficially affected by the insertion of silicone substituents and that the introduction of well-chosen silicone motifs is an excellent strategy for agrochemical research.

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Section: Resultsmentioning

confidence: 99%

Design, Synthesis, and Properties of Silicon-Containing meta-Diamide Insecticides

Quan

et al. 2023

J. Agric. Food Chem.

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“…[5] More recently, the carbon atom substitution was pushed further and the next crystallogen element, germanium, attracted attention. The C/Ge swap that goes with a further increase of the covalent radius, lipophilicity, and electropositivity was rapidly applied to bioactive compounds [6][7] as well as perfume ingredients or in the design of fungicides. [8] The group of Tacke has been one of the main contributors in the field and this laboratory published among the most remarkable examples (Figure 1).…”

Section: Introductionmentioning

confidence: 99%

Anionic Access to Silylated and Germylated Binuclear Heterocycles

Boddaert

Colleoni

Mistico

et al. 2014

Chemistry A European J

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A simple access to silylated and germylated binuclear heterocycles, based on an original anionic rearrangement, is described. A set of electron-rich and electron-poor silylated aromatic and heteroaromatic substrates were tested to understand the mechanism and the factors controlling this rearrangement, in particular its regioselectivity. This parameter was shown to follow the rules proposed before from a few examples. Then, the effect of the substituents borne by the silicon itself, in particular the selectivity of the ligand transfer, was studied. Additionally, this chemistry was extended to germylated substrates. A hypervalent germanium species, comparable to the putative intermediate proposed with silicon, seems to be involved. However, a pathway implicating the elimination of LiCH2Cl was observed for the first time with this element, leading to unexpected products of the benzo-oxa (or benzo-aza) germol-type.

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“…Bioisosteric replacement has been demonstrated as a successful strategy in pharmaceutical and agrochemical research. − Silicon is a logical choice as a carbon isostere, ,,,,,− because they are one below the other in the periodic table and both have four valence electrons each; however, the chemical and physical differences that the silyl group introduces can endow compounds with unique properties. For example, the larger radius of the tetravalent silicon center can alter ligand–receptor interactions, and the increased lipophilicity of organosilicon molecules can improve cell and tissue penetration.…”

Section: Introductionmentioning

confidence: 99%

Silicon-Containing Complex II Acaricides─Design, Synthesis, and Pharmacological Optimization

Zhou

Wang

Quan

et al. 2022

J. Agric. Food Chem.

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Bioisosteric replacement has been proven to be a powerful strategy in life science research. In this review, general aspects of carbon–silicon bioisosteric substitution and its applications in pharmaceutical and crop protection research are described. Carbon and their silicon analogues possess similar intrinsic properties. Replacing carbon with silicon in pharmaceuticals and pesticides has shown to result in positive effects on efficacy and selectivity, physicochemical properties, and bioavailability and also to eliminate or improve human or environmental safety properties as well as to provide novelty and new intellectual property in many cases. Furthermore, the application of carbon–silicon substitution in the search for new complex II acaricides is highlighted. This research led to the discovery of sila-cyflumetofen 23a and other silicon-containing analogues of cyflumetofen that match or exceed the acaricidal activity of cyflumetofen. The molecular design strategy, synthetic aspects, biological activity, computational modeling work, and structure–activity relationships will be discussed.

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Bioorganogermanium Chemistry: Studies on C/Si/Ge Bioisosterism

Cited by 26 publications

References 16 publications

Design, Synthesis, and Properties of Silicon-Containing meta-Diamide Insecticides

Design, Synthesis, and Properties of Silicon-Containing meta-Diamide Insecticides

Anionic Access to Silylated and Germylated Binuclear Heterocycles

Silicon-Containing Complex II Acaricides─Design, Synthesis, and Pharmacological Optimization

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