Orthogonal bioconjugation targeting cysteine-containing peptides and proteins using alkyl thianthrenium salts DOI Creative Commons

Guangjun Bao,

Xinyi Song,

Yiping Li

и другие.

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Авг. 12, 2024

Late-stage specific and selective diversifications of peptides proteins performed at target residues under ambient conditions are recognized to be the most facile route various abundant conjugates. Herein, we report an orthogonal modification cysteine using alkyl thianthreium salts, which proceeds with excellent chemoselectivity compatibility mild conditions, introducing a diverse array functional structures. Crucially, multifaceted bioconjugation is achieved through clickable handles incorporate structurally molecules. This "two steps, one pot" method successfully applied label bovine serum albumin. Therefore, our technique versatile powerful tool for late-stage bioconjugation. modifications routes bioconjugates. Here, authors

Язык: Английский

A Perspective on Late-Stage Aromatic C–H Bond Functionalization DOI Creative Commons
Li Zhang, Tobias Ritter

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(6), С. 2399 - 2414

Опубликована: Янв. 27, 2022

Late-stage functionalization of C-H bonds (C-H LSF) can provide a straightforward approach to the efficient synthesis functionalized complex molecules. However, LSF is challenging because bond must be in presence various other functional groups. In this Perspective, we evaluate aromatic on basis four criteria─reactivity, chemoselectivity, site-selectivity, and substrate scope─and our own views current challenges as well promising strategies areas growth going forward.

Язык: Английский

Процитировано

235
Sustainable Thioetherification via Electron Donor–Acceptor Photoactivation Using Thianthrenium Salts DOI
María Jesús Cabrera‐Afonso, Albert Granados,

Gary A. Molander

и другие.

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(22)

Опубликована: Март 16, 2022

Abstract The synthesis of sulfides has been widely studied because this functional subunit is prevalent in biomolecules and pharmaceuticals, as well being a useful synthetic platform for further elaboration. Thus, various methods to build C−S bonds have developed, but typically they require the use precious metals or harsh conditions. Electron donor–acceptor (EDA) complex photoactivation strategies emerged versatile sustainable ways achieve bond formation, avoiding challenges associated with previous methods. This work describes an open‐to‐air, photoinduced, site‐selective C−H thioetherification from readily available reagents via EDA formation that tolerates wide range different groups. Moreover, C(sp 2 )−halogen remain intact using protocol, allowing late‐stage installation sulfide motif bioactive scaffolds, while yet modification through more traditional C−X cleavage protocols. Additionally, mechanistic investigations support envisioned scenario.

Язык: Английский

Процитировано

139
A general electron donor–acceptor complex for photoactivation of arenes via thianthrenation DOI Creative Commons
Kai Sun,

Anzai Shi,

Yan Liu

и другие.

Chemical Science, Год журнала: 2022, Номер 13(19), С. 5659 - 5666

Опубликована: Янв. 1, 2022

General photoactivation of EDA complexes between arylsulfonium salts and 1,4-diazabicyclo[2.2.2]octane was discovered. This practical mode enables the generation aryl radicals for C–H functionalization arenes.

Язык: Английский

Процитировано

132
Organothianthrenium salts: synthesis and utilization DOI Creative Commons
Huan Meng, Ming‐Shang Liu, Wei Shu

и другие.

Chemical Science, Год журнала: 2022, Номер 13(46), С. 13690 - 13707

Опубликована: Янв. 1, 2022

This review summarizes the synthesis of diverse organothianthrenium salts from various precursors and their applications in organic to forge new C–C, C–H C–heteroatom bonds by C–S bond cleavage with different mechanistic considerations.

Язык: Английский

Процитировано

132
Transition Metal-Catalyzed Biaryl Atropisomer Synthesis via a Torsional Strain Promoted Ring-Opening Reaction DOI
Xue Zhang, Kun Zhao, Zhenhua Gu

и другие.

Accounts of Chemical Research, Год журнала: 2022, Номер 55(12), С. 1620 - 1633

Опубликована: Июнь 1, 2022

ConspectusArising from the restricted rotation of a single bond caused by steric or electronic effects, atropisomerism is one few fundamental categories for molecules to manifest their three-dimensional characters into which axially chiral biaryl compounds fall. Despite widespread occurrence skeletons in natural products, bioactive molecules, and ligands/organocatalysts, catalytic asymmetric methods synthesis these structures still lag behind demand. Major challenges preparation biaryls include accessing highly sterically hindered variants while controlling stereoselectivity. A couple useful strategies have emerged direct last two decades.Recently, we engaged atropisomers via transition metal catalysis, including ring-openings dibenzo cyclic compounds. During studies, serendipitously discovered that substituents adjacent axis cause be distorted minimize repulsion. The display higher reactivity ring-opening reactions than non-distorted molecules. In other words, torsional strain can promote reaction. On basis this concept, successfully realized reaction diaryliodoniums, silanes, 9H-fluoren-9-ols, delivered several differently substituted ortho tetra-substituted high enantioselectivity. not only activates substrates toward under mild conditions but also changes chemoselectivity bond-breaking events. palladium-catalyzed carboxylation S-aryl dibenzothiophenium, inversed selectivity exocyclic C–S cleavage reaction.In Account, summarize our studies on copper-, rhodium-, as collection straightforward with enantiopurity above-mentioned strain-promoted coupling strategy. part, energies are discussed aid density functional theory (DFT) calculations.

Язык: Английский

Процитировано

126
Cu-Mediated Thianthrenation and Phenoxathiination of Arylborons DOI
Xiaoyue Chen, Yaning Li, Yichen Wu

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(18), С. 10431 - 10440

Опубликована: Апрель 26, 2023

Great success in synthetic chemistry is motivated by the development of novel and reactive linchpins for carbon-carbon carbon-heteroatom bond formation reactions, which has dramatically altered chemists' approach to building molecules. Herein, we report ready synthesis aryl sulfonium salts, a versatile electrophilic linchpin, via Cu-mediated thianthrenation phenoxathiination commercially available arylborons with thianthrene phenoxathiine, providing series salts high efficiency. More importantly, leveraging sequential Ir-catalyzed C-H borylation arylborons, formal arenes also achieved. The undirected normally occurred at less steric hindrance position, thus complementary method comparison thianthrenation. This process capable late-stage functionalization pharmaceuticals, might find wide applications both industry academic sectors.

Язык: Английский

Процитировано

57
Nickel Meets Aryl Thianthrenium Salts: Ni(I)-Catalyzed Halogenation of Arenes DOI Creative Commons
Shengyang Ni, Jiyao Yan,

Srija Tewari

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(18), С. 9988 - 9993

Опубликована: Май 1, 2023

Herein, a regioselective, late-stage two-step arene halogenation method is reported. We propose how unusual Ni(I)/(III) catalysis enabled by combination of aryl thianthrenium and Ni redox properties that hitherto unachieved with other (pseudo)halides. The catalyst accessed in situ from inexpensive NiCl2·6(H2O) zinc without the need supporting ligands.

Язык: Английский

Процитировано

57
Standardized Approach for Diversification of Complex Small Molecules via Aryl Thianthrenium Salts DOI Creative Commons
Dilgam Ahmadli, Sven Müller, Yuanhao Xie

и другие.

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Янв. 21, 2025

Thianthrenation is a useful strategy for the late-stage diversification of complex small molecules owing to positional selectivity and synthetic versatility thianthrenium salts as electrophilic linchpins. However, substrate-dependent identification suitable reaction conditions thianthrenation can be difficult. Reported functionalization vary significantly and, in some instances, lack robustness practicality. Herein, we report generalized approach preparation two manifolds practical, robust, parallel salts.

Язык: Английский

Процитировано

4
Vinyl Thianthrenium Tetrafluoroborate: A Practical and Versatile Vinylating Reagent Made from Ethylene DOI Creative Commons
Fabio Juliá, Jiyao Yan, Fritz Paulus

и другие.

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(33), С. 12992 - 12998

Опубликована: Авг. 10, 2021

The use of vinyl electrophiles in synthesis has been hampered by the lack access to a suitable reagent that is practical and appropriate reactivity. In this work we introduce thianthrenium salt as an effective vinylating reagent. bench-stable, crystalline can be readily prepared from ethylene gas at atmospheric pressure one step broadly useful annulation chemistry (hetero)cycles, N-vinylation heterocyclic compounds, palladium-catalyzed cross-coupling reactions. structural features thianthrene core enable distinct reactivity profile, unprecedented for other sulfonium derivatives.

Язык: Английский

Процитировано

97
High Site Selectivity in Electrophilic Aromatic Substitutions: Mechanism of C–H Thianthrenation DOI Creative Commons
Fabio Juliá, Qianzhen Shao, Meng Duan

и другие.

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(39), С. 16041 - 16054

Опубликована: Сен. 21, 2021

The introduction of thianthrene as a linchpin has proven to be versatile strategy for the C–H functionalization aromatic compounds, featuring broad scope and fast diversification. synthesis aryl thianthrenium salts displayed an unusually high para regioselectivity, notably superior those observed in halogenation or borylation reactions various substrates. We report experimental computational study on mechanism thianthrenation reactions, with emphasis elucidation reactive species nature exquisite site selectivity. Mechanisms involving direct attack arene isolated O-trifluoracetylthianthrene S-oxide (TT+-TFA) dication (TT2+) via electron transfer under acidic conditions are identified. A reversible interconversion different Wheland-type intermediates before subsequent, irreversible deprotonation is proposed responsible exceptional selectivity reaction.

Язык: Английский

Процитировано

90