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

Triply Selective & Sequential Diversification at Csp3: Expansion of Alkyl Germane Reactivity for C−C & C−Heteroatom Bond Formation DOI Creative Commons

Eric Ahrweiler,

Markus D. Schoetz,

Gurdeep Singh

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(16)

Published: Feb. 22, 2024

Abstract We report the triply selective and sequential diversification of a single C sp 3 carbon carrying Cl, Bpin GeEt for modular programmable construction ‐rich molecules. Various functionalizations −Cl −BPin (e.g. alkylation, arylation, homologation, amination, hydroxylation) were tolerated by −GeEt group. Moreover, methodological repertoire alkyl germane functionalization was significantly expanded beyond hitherto known Giese addition arylation to alkynylation, alkenylation, cyanation, halogenation, azidation, C−S bond formation as well first demonstration stereo‐selective ‐[Ge] bond.

Language: Английский

Citations

6
Photoredox Nickel‐Catalysed Stille Cross‐Coupling Reactions DOI Creative Commons
Zhenghong Zhou, Jimin Yang, Bo Yang

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(52)

Published: Nov. 10, 2023

The Stille cross-coupling reaction is one of the most common strategies for construction C-C bonds. Despite notable strides in advancement reaction, persistent challenges persist hindering its greener evolution. These encompass multiple facets, such as high cost precious metals and ligands, demand various additives, slow rate. In comparison to dominant palladium-catalysed reactions, cost-effective nickel-catalysed systems lag behind, enantioconvergent reactions racemic stannanes remain undeveloped. Herein, we present a pioneering instance stannane reagents, resulting formation bonds good yields with excellent stereoselectivity. This strategy provides practical, scalable, operationally straightforward method synthesis C(sp3 )-C(sp3 ), )-C(sp2 )-C(sp) under exceptionally mild conditions (without additives bases, ambient temperature). innovative use synergistic photoredox/nickel catalysis enables novel single-electron transmetalation process providing new research paradigm reactions.

Language: Английский

Citations

13
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

12
Electrochemistry-Enabled C-Heteroatom Bond Formation of Alkyl Germanes DOI

Markus D. Schoetz,

Kristina Deckers,

Gurdeep Singh

et al.

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

Citations

5
Photochemical Synthesis of S,N,O-Containing Polyheterocycles via an α-C(sp3)–H Functionalization/Radical Cyclization Cascade DOI

Shiyan Cheng,

Jia-Bin Liao,

Yu‐Mei Lin

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(35), P. 6566 - 6570

Published: Aug. 30, 2023

A highly effective approach based on an organophotocatalytic α-C(sp3)-H functionalization/radical cyclization cascade has been developed. This method enables the synthesis of various tricyclic heterocycles containing S, O, and N atoms with excellent site selectivity diastereoselectivity. Mechanistic investigations have confirmed that reaction involves photoredox-triggered C(sp3)-H cleavage followed by a radical aromatization process. These findings are expected to pave way for developing cost-effective tandem reactions synthesizing heterocyclic drugs.

Language: Английский

Citations

10
Orthogonal sp3‐Ge/B Bimetallic Modules: Enantioselective Construction and Enantiospecific Cross‐Coupling DOI
Mengyu Xu, Weitao Jiang,

Ming‐Zhi Xia

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(16)

Published: Feb. 12, 2024

Abstract In this study, a series of enantioenriched sp 3 ‐Ge/B bimetallic modules were successfully synthesized via an enantioselective copper‐catalyzed hydroboration carbagermatrane ( Ge )‐containing alkenes. Orthogonal cross‐coupling selectivity under different Pd‐catalyzed conditions was achieved in enantiospecific manner. Notably, the chiral secondary exhibited remarkable transmetallation ability prior to primary or Bpin. The effectiveness Ge/B strategy further demonstrated through development new functional small molecules with Aggregation‐Induced Emission (AIE) and Circularly Polarized Luminescence (CPL) performance. This represents first successful example synthesis alkylgermanium reagents that permit reactions.

Language: Английский

Citations

4
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
Access to germasiloxanes and alkynylgermanes mediated by earth-abundant species DOI Creative Commons
Hanna Stachowiak, Krzysztof Kuciński, Konstancja Broniarz

et al.

Scientific Reports, Journal Year: 2023, Volume and Issue: 13(1)

Published: April 6, 2023

The reactions between silanols or terminal acetylenes with alkynylgermanes have been accomplished using potassium bis(trimethylsilyl)amide as the catalyst. This strategy has provided an entry point into various organogermanes including germasiloxanes and alkynylgermanes. Remarkably, not only KHMDS but also simple bases such KOH can serve efficient catalysts in this process.

Language: Английский

Citations

9
Redox-Neutral Photocatalytic Germylative Difunctionalization of Unactivated Olefins via Selective Radical Capture by Ge(II) DOI
Wenjing Zhou, Zequn Yang, Bin Xiao

et al.

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

Citations

0
Unlocking the Reactivity of the C-In Bond: Alkyl Indium Reagents as a Source of Radicals Under Photocatalytic Conditions DOI Creative Commons
Anton A. Gladkov, Vitalij V. Levin,

Demian Y. Cheboksarov

et al.

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Generation of organic radicals from organometallic compounds is a key step in metallaphotoredox cross-coupling reactions. The ability organoindium to serve as sources alkyl under light promoted oxidative conditions described. Organoindium reagents were used dual photocatalytic/nickel with aryl bromides. These can be conveniently obtained primary, secondary and tertiary bromides chlorides using novel indium(i) bromide/lithium bromide system. Both steps, the formation organoindiums their are insensitive towards air moisture tolerate wide variety functional groups.

Language: Английский

Citations

0