Recent Developments with Organogermanes: their Preparation and Application in Synthesis and Catalysis DOI Creative Commons
Tatiana Rogova,

Eric Ahrweiler,

Markus D. Schoetz

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 136(8)

Published: Oct. 30, 2023

Abstract Within the sphere of traditional Pd 0 /Pd II cross coupling reactions, organogermanes have been historically outperformed both in terms scope and reactivity by more conventional transmetalating reagents. Subsequently, this class compounds has largely underutilized as a partner bond‐forming strategies. Most recent studies, however, shown that alternative modes activation these notoriously robust building blocks transform into most reactive site molecule—capable outcompeting other functional groups (such boronic acids, esters silanes) for C−C C–heteroatom bond formation. As result, over past few years, literature increasingly featured methodologies explore potential chemoselective orthogonal partners. Herein we highlight some advances field organogermane chemistry with respect to their synthesis applications synthetic catalytic transformations.

Language: Английский

Chemoselective Heterogeneous Hydrogenation of Sulfur Containing Quinolines under Mild Conditions DOI Creative Commons

Lukas Lückemeier,

Thijs De Vos,

Lisa Schlichter

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(9), P. 5864 - 5871

Published: Feb. 20, 2024

Sulfur, alongside oxygen and nitrogen, holds a prominent position as one of the key heteroatoms in nature medicinal chemistry. Its significance stems from its ability to adopt different oxidation states, rendering it valuable both polarity handle hydrogen bond donor/acceptor. Nevertheless, poisonous free electron pairs makes sulfur containing substrates inaccessible for many catalytic protocols. Strong (at low temperatures) irreversible chemisorption catalyst's surface is particular detrimental heterogeneous catalysts, possessing only few catalytically active sites. Herein, we present novel Ru-S catalyst that tolerates multiple functionalities, including thioethers, thiophenes, sulfoxides, sulfones, sulfonamides, sulfoximines, hydrogenation quinolines. The utility products was further demonstrated by subsequent diversifications functionalities.

Language: Английский

Citations

18
Recent Developments with Organogermanes: their Preparation and Application in Synthesis and Catalysis DOI Creative Commons
Tatiana Rogova,

Eric Ahrweiler,

Markus D. Schoetz

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(8)

Published: Oct. 30, 2023

Within the sphere of traditional Pd

Language: Английский

Citations

24
Hydrogenation of functionalised pyridines with a rhodium oxide catalyst under mild conditions DOI Creative Commons
Sydney Williams,

Leiming Qi,

Robert J. Cox

et al.

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(5), P. 1010 - 1017

Published: Jan. 1, 2024

The commercially available, easy-to-handle Rh 2 O 3 catalyses the hydrogenation of functionalised pyridines under mild conditions.

Language: Английский

Citations

6
Arene Reduction by Rh/Pd or Rh/Pt under 1 atm Hydrogen Gas and Room Temperature DOI
Hanxiao Li, Zhi‐Xiang Yu

Organic Letters, Journal Year: 2024, Volume and Issue: 26(16), P. 3458 - 3462

Published: April 17, 2024

Current methods for arene hydrogenation generally need either harsh reaction conditions or complex catalyst preparation. Here we describe a mild and convenient protocol that only utilizes commercially available catalysts. Using [Rh(nbd)Cl]2 Pd/C together as catalysts, arenes bearing various functional groups can be hydrogenated under 1 atm of H2 at room temperature. This also achieved using catalysts [Rh(cod)Cl]2 PtO2, thus avoiding glovebox manipulations simplifying the procedure.

Language: Английский

Citations

5
Ni-catalyzed reductive alkylgermylation of activated alkenes: Modular access to polyfunctionalized alkyl germanes DOI Creative Commons

Yi-Wei Qiao,

Bing-Qi Zhou,

Yuan Huang

et al.

Chem Catalysis, Journal Year: 2023, Volume and Issue: 3(12), P. 100819 - 100819

Published: Nov. 22, 2023

Language: Английский

Citations

11
Visible‐Light‐Driven Germyl Radical Generation via EDA‐Catalyzed ET–HAT Process DOI Creative Commons

Kaito Yoshizawa,

Bi‐Xiao Li, Taro Matsuyama

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(41)

Published: May 8, 2024

Abstract We have established a facile and efficient protocol for the generation of germyl radicals by employing photo‐excited electron transfer (ET) in an donor‐acceptor (EDA) complex to drive hydrogen‐atom (HAT) from hydride (R 3 GeH). Using catalytic amount EDA commercially available thiol benzophenone derivatives, ET‐HAT cycle smoothly proceeds simply upon blue‐light irradiation without any transition metal or photocatalyst. This also affords silyl radical hydride.

Language: Английский

Citations

4
Synthetic techniques for thermodynamically disfavoured substituted six-membered rings DOI

Yangyang Li,

Hongjin Shi,

Guoyin Yin

et al.

Nature Reviews Chemistry, Journal Year: 2024, Volume and Issue: 8(7), P. 535 - 550

Published: May 31, 2024

Language: Английский

Citations

4
Photocatalytic Germylation via Direct Hydrogen Atom Transfer DOI

Wenshan Wang,

Yan Liu,

Qiang Gao

et al.

Chinese Journal of Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 18, 2025

Comprehensive Summary An innovative visible‐light‐driven direct hydrogen atom transfer ( d ‐HAT) of Ge–H bond has been developed, wherein the photoexcited 9,10‐phenanthraquinone PC HAT 9 ) serves as an efficient photocatalyst for generation germanium‐centered radicals from germanium hydrides including Ph 3 GeH, n Bu and 2 GeH . By employing hypervalent iodine reagents SOMOphiles, this protocol facilitates streamlined germylation through a mechanism involving germyl radical addition followed by β‐cleavage carboxyl to yield diverse array ethynyl‐, vinyl‐, nitrile‐, phenyl‐functionalized germanes. The methodological leap signifies noteworthy departure previous photocatalytic indirect i relying on combined usage SET with abstractors, which not only advances methodology creating in fashion but also provides access structurally novel pharmaceutically promising organogermanium compounds that are difficult synthesize routine methods.

Language: Английский

Citations

0
Site‐Isolated Rhodium(II) Metalloradicals Catalyze Olefin Hydrofunctionalization DOI Creative Commons
Zihang Qiu, Hao Deng, Constanze N. Neumann

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(18)

Published: Feb. 7, 2024

Abstract Rh(II) porphyrin complexes display pronounced metal‐centered radical character and the ability to activate small molecules under mild conditions, but catalysis with porphyrins is extremely rare. In addition facile dimerization, readily engage in kinetically thermodynamically reactions involving two centers generate stable Rh(III)−X intermediates that obstruct turnover thermal catalysis. Here we report site isolation of metalloradicals a MOF host, which not only protects against also allows them participate Access PCN‐224 or PCN‐222 linkers are fully metalated by absence any accompanying Rh(0) nanoparticles was achieved via first direct synthesis linker containing transition‐metal alkyl moiety, followed Rh(III)−C bond photolysis.

Language: Английский

Citations

3
Visible-Light-Driven Silyl or Germyl Radical Generation via Si–C or Ge–C Bond Homolysis DOI
Bi‐Xiao Li, H. Ishida, Chao Wang

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(10), P. 1765 - 1770

Published: March 8, 2023

We report a simple, rapid, and selective protocol for visible-light-driven generation of silyl radicals through photoredox-induced Si-C bond homolysis. Irradiating 3-silyl-1,4-cyclohexadienes with blue light in the presence commercially available photocatalyst smoothly generated bearing various substituents within 1 h, these were trapped by broad range alkenes to afford products good yields. This process is also efficient germyl radicals.

Language: Английский

Citations

8