Enantio- and Regioconvergent Synthesis of γ-Stereogenic Vinyl Germanes and Their Use as Masked Vinyl Halides DOI
Daniel Brösamlen, Martin Oestreich

Organic Letters, Journal Year: 2023, Volume and Issue: 25(11), P. 1901 - 1906

Published: March 9, 2023

A nickel-catalyzed enantio- and regioconvergent alkylation of regioisomeric mixtures racemic germylated allylic electrophiles with alkyl nucleophiles is reported. Key to success a newly developed hept-4-yl-substituted Pybox ligand that enables accessing various chiral γ-germyl α-alkyl building blocks in excellent yields enantioselectivities. The reason for the regioconvergence steering effect bulky germyl group. resulting vinyl germanes can be easily halodegermylated without racemization stereocenter afford synthetically valuable γ-stereogenic halides.

Language: Английский

Construction of Hydrazone-Linked Macrocycle-Enriched Covalent Organic Frameworks for Highly Efficient Photocatalysis DOI
Menghao Li, Zhiqiang Yang, Zheng Li

et al.

Chemistry of Materials, Journal Year: 2022, Volume and Issue: 34(12), P. 5726 - 5739

Published: June 9, 2022

Covalent organic frameworks (COFs) are an emerging class of crystalline porous materials with tailor-made functionalities for improved photocatalytic activity. However, limited choice building blocks greatly restricts the photochemical performance and application scope COFs in photocatalysis. Herein, a covalent hybridization approach is reported to address these issues by knitting rigid macrocyclic struts, namely, pillararenes, into extended network COFs. Varying different ratios pillararenes unique conformations electron-rich cavities can not only generate confined molecular space exciton migration carrier transport but also create new interfaces interplay photogenerated charge carriers, leading high promoting efficient oxidation amines imines. This work paves way constructing macrocycle-derived provides promising platform photocatalysis through predesign functionalization pore surface.

Language: Английский

Citations

59
Three-Component Cross-Electrophile Coupling: Regioselective Electrochemical Dialkylation of Alkenes DOI
Lingxiang Lu, Yi Wang,

Wendy Zhang

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(41), P. 22298 - 22304

Published: Oct. 6, 2023

The cross-electrophile dialkylation of alkenes enables the formation two C(sp

Language: Английский

Citations

35
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

26
Photogeneration of α-Bimetalloid Radicals via Selective Activation of Multifunctional C1 Units DOI Creative Commons

Lewis McGhie,

Alessandro Marotta,

Patrick O. Loftus

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(23), P. 15850 - 15859

Published: May 28, 2024

Light-driven strategies that enable the chemoselective activation of a specific bond in multifunctional systems are comparatively underexplored comparison to transition-metal-based technologies, yet desirable when considering controlled exploration chemical space. With current drive discover next-generation therapeutics, reaction design enables strategic incorporation an sp3 carbon center, containing multiple synthetic handles for subsequent space would be highly enabling. Here, we describe photoactivation ambiphilic C1 units generate α-bimetalloid radicals using only Lewis base and light source directly activate C–I bond. Interception these transient with various SOMOphiles rapid synthesis organic scaffolds (B, Si, Ge) orthogonal activation. In-depth theoretical mechanistic studies reveal prominent role 2,6-lutidine forming photoactive charge transfer complex stabilizing situ generated iodine radicals, as well influential boron p-orbital activation/weakening This simple efficient methodology enabled expedient access functionalized 3D frameworks can further derivatized available technologies C–B C–Si

Language: Английский

Citations

14
Organobismuth Compounds as Aryl Radical Precursors via Light-Driven Single-Electron Transfer DOI
Nicholas D. Chiappini, Eric P. Geunes,

Ethan T. Bodak

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(4), P. 2664 - 2670

Published: Feb. 6, 2024

A light-driven method for the generation of aryl radicals from triarylbismuth(III) and (V) reagents is described. Aryl radical proposed to occur through ligand-assisted mesolytic cleavage an organobismuth(IV) intermediate generated either oxidation BiIII or reduction BiV. This mode demonstrated be compatible with a range bimolecular arylations, including hydroarylation electron-deficient olefins arylation diboronates, disulfides, sulfonyl cyanides, phosphites, isocyanides. The intermediacy supported by trapping clock experiments, BiIV–aryl mesolysis computationally.

Language: Английский

Citations

10
Advances in Transition‐Metal‐Catalyzed Hydrogermylation of Alkenes and Alkynes† DOI

Zungui Zhao,

Furen Zhang, Dongyang Wang

et al.

Chinese Journal of Chemistry, Journal Year: 2023, Volume and Issue: 41(22), P. 3063 - 3081

Published: June 10, 2023

Comprehensive Summary Hydrogermylation of alkenes and alkynes provides a straightforward synthetic route to organogermanium compounds that have been found applications in organic synthesis, medicinal chemistry, material science. This paper reviews the advances transition‐metal‐catalyzed hydrogermylation unsaturated carbon‐carbon bonds, including alkenes, alkynes, dienes, allenes, with objective providing readers status field. Progress, problems, perspectives this field are discussed.

Language: Английский

Citations

20
cis-Selective Hydrogenation of Aryl Germanes: A Direct Approach to Access Saturated Carbo- and Heterocyclic Germanes DOI Creative Commons
Akash Kaithal, Himadri Sekhar Sasmal, Subhabrata Dutta

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(7), P. 4109 - 4118

Published: Feb. 13, 2023

A catalytic approach of synthesizing the cis-selective saturated carbo- and heterocyclic germanium compounds (3D framework) is reported via hydrogenation readily accessible aromatic germanes (2D framework). Among numerous catalysts tested, Nishimura's catalyst (Rh2O3/PtO2·H2O) exhibited best reactivity with an isolated yield up to 96%. broad range substrates including synthesis unprecedented was explored. This selective strategy could tolerate several functional groups such as −CF3, −OR, −F, −Bpin, −SiR3 groups. The synthesized products demonstrated applications in coupling reactions newly developed aza-Giese-type addition reaction (C–N bond formation) from cyclic germane product. These versatile motifs can have a substantial value organic medicinal chemistry they show orthogonal while competing other partners boranes or silanes, acquiring three-dimensional structure high stability robustness.

Language: Английский

Citations

19
trans-Ge/B 1,1-Hydroboration of Alkynylgermanes with 9-BBN DOI

Zi‐Long An,

Chao Chen, Alice Yu

et al.

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

Citations

1
Organogermanium(iv) compounds in photo-induced radical reactions DOI

Qing‐Hao Xu,

Bin Xiao

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(24), P. 7016 - 7027

Published: Jan. 1, 2022

Behaviors of typical organogermanium( iv ) compounds in photo-induced reactions are reviewed.

Language: Английский

Citations

24
Anti-Markovnikov Hydrogermylation of Alkenes via Lewis Acid Catalysis DOI
Franziska Schoenebeck,

Aymane Selmani

Synthesis, Journal Year: 2023, Volume and Issue: 55(11), P. 1792 - 1798

Published: Feb. 15, 2023

Abstract The direct hydrogermylation of alkenes under Lewis acid catalysis is reported. use borane B(C6F5)3 as a catalyst allows for mild, metal-free and concomitant reduction ketones aldehydes. Regardless electronic biases, anti-Markovnikov observed in high yields. Moreover, the process scalable proceeds mild conditions at room temperature.

Language: Английский

Citations

14