trans-Ge/B 1,1-Hydroboration of Alkynylgermanes with 9-BBN

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 23, 2025

A 1,1-hydroboration of alkynylgermanes with unique trans-Ge/B stereochemistry under transition-metal-free conditions is reported. Mechanistic studies suggest that a pathway involving α-boration followed by stepwise 1,2-Ge/H shift on the intermediate structurally lies between an alkyne-Ge+ π complex and typical vinyl cation. The resulting Ge/B bimetallic modules, along Ge*/Ge/B trimetallic variant, can be conveniently transformed into trisubstituted olefins through iterative divergent cross-coupling. This work demonstrates incorporating metalloids classical organic reactions may offer unconventional chemical selectivity efficient synthetic applications.

Language: Английский

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Electrochemistry-Enabled C-Heteroatom Bond Formation of Alkyl Germanes

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(31), P. 21257 - 21263

Published: July 26, 2024

Because of their robustness and orthogonal reactivity features, alkyl germanes bear significant potential as functional handles for the construction C(sp3)-rich scaffolds, especially in context modular synthetic approaches. However, to date, only radical-based has been accessible from these handles, which limits types possible decorations. Here, we describe first general C(sp3)–heteroatom bond formation (−GeEt3) by leveraging electrochemistry unlock polar reactivity. This approach allowed us couple C(sp3)–GeEt3 with a variety nucleophiles construct ethers, esters, amines, amides, sulfonamides, sulfides, well C–P, C–F, C–C bonds. The compatibility electrochemical strategy C1 motif was also showcased, involving sequential functionalization Cl, Bpin, ultimately GeEt3 via electrochemistry.

Language: Английский

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Redox-Neutral Photocatalytic Germylative Difunctionalization of Unactivated Olefins via Selective Radical Capture by Ge(II)

ACS Catalysis, Journal Year: 2025, Volume and Issue: 15(3), P. 2150 - 2157

Published: Jan. 22, 2025

This study reports the development of a photocatalytic germanyl functionalization unactivated olefins. A modular approach to alkylgermanium trihalides was realized through three-component radical reaction involving fluoroalkyl bromides and commercially available GeBr2 in redox-neutral process. The target organogermanes were readily obtained via one-pot derivatization using various Grignard reagents, demonstrating good functional group compatibility with amides, esters ketones. work highlights utility Ge(II) reagents constructing C–Ge bonds photoredox catalysis. Notably, selectivity capturing electrophilic or nucleophilic radicals by found be significantly influenced halide ligands on GeX2.

Language: Английский

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Photoinduced Palladium-Catalyzed Radical Germylative Arylation of Alkenes with Chlorogermanes

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(17), P. 12848 - 12852

Published: Aug. 15, 2024

We describe a visible light-induced palladium-catalyzed radical germylative arylation of alkenes with easily accessible chlorogermanes. This protocol provides expedient access to germanium-substituted indolin-2-ones in good excellent yields under mild reaction conditions. The key step for this strategy lies the reductive activation germanium–chloride bonds an excited palladium complex light irradiation. involvement germanium radicals was evidenced by electron paramagnetic resonance spectroscopy experiments.

Language: Английский

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Toward Multi‐Functionalized Organogermaniums: Diastereoselective Transformations of Germacycles Derived from Cheletropic Reactions of Boron‐Substituted Butadienes with Ge(II) Salts

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 22, 2024

Abstract The field of organogermanium in chemistry has recently attracted attention. Thanks to the inherent features germanium (Ge), introducing Ge‐based substituents into organic frameworks enhanced bioactivity and optoelectronic properties molecules. Herein, synthesis multi‐functionalized organogermaniums using Ge(II) salts is reported. germacycles having an allylboron moiety, which derived from (4+1) cycloadditions butadienes bearing a boronic ester moiety with salts, can be applied further allylboration aldehydes perfect diastereoselectivity. obtained allylated adducts enable access π‐extended retention stereocenters.

Language: Английский

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Bis(triazole) derivatives of organodigermanes: synthesis, structure, and properties

Mendeleev Communications, Journal Year: 2024, Volume and Issue: 34(6), P. 819 - 821

Published: Nov. 1, 2024

Language: Английский

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