A Porphyrin Iron(III) π‐Dication Species and its Relevance in Catalyst Design for the Umpolung of Nucleophiles DOI Creative Commons
Silène Engbers, Yisong Guo, Johannes E. M. N. Klein

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(46)

Published: Sept. 25, 2023

Abstract Isoporphyrins have recently been identified as remarkable species capable of turning the nucleophile attached to porphyrin ring into an electrophile, thereby providing umpolung reactivity ( Inorg. Chem . 2022 , 61 8105–8111). They are generated by nucleophilic attack on iron(III) π‐dication, a class that has received scant attention. Here, we explore effect meso ‐substituent and report π‐dication bearing ‐tetraphenylporphyrin (TPP) ligand. We provide extensive study UV/Vis absorption, 2 H NMR, EPR, applied field Mössbauer, resonance Raman spectroscopy. further system's highly dynamic tunable properties address nature axial ligands well conformation ring. The insights presented essential for rational design catalysts nucleophiles. Such catalytic avenues could example novel method electrophilic chlorinations. examine importance electronic tuning factor in catalyst design.

Language: Английский

Metal-free photocatalytic cross-electrophile coupling enables C1 homologation and alkylation of carboxylic acids with aldehydes DOI Creative Commons
Stefano Bonciolini, Antonio Pulcinella, Matteo Leone

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Feb. 19, 2024

In contemporary drug discovery, enhancing the sp

Language: Английский

Citations

19
Acetal‐thiol Click‐like Reaction: Facile and Efficient Synthesis of Dynamic Dithioacetals and Recyclable Polydithioacetals DOI

Shuai Du,

Shuaiqi Yang,

Binbo Wang

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(31)

Published: May 20, 2024

Dithioacetals are heavily used in organic, material and medical chemistries, exhibit huge potential to synthesize degradable or recyclable polymers. However, the current synthetic approaches of dithioacetals polydithioacetals overwhelmingly dependent on external catalysts organic solvents. Herein, we disclose a catalyst- solvent-free acetal-thiol click-like reaction for synthesizing polydithioacetals. High conversion, higher than acid catalytic reaction, can be achieved. universality was confirmed by monitoring reactions linear cyclic acetals (including renewable bio-sourced furan-acetal) with aliphatic aromatic thiols, mechanism monomolecular nucleophilic substitution (S

Language: Английский

Citations

12
Fast Cysteine Bioconjugation Chemistry DOI Creative Commons
Fa‐Jie Chen, Jianmin Gao

Chemistry - A European Journal, Journal Year: 2022, Volume and Issue: 28(66)

Published: Aug. 16, 2022

Cysteine bioconjugation serves as a powerful tool in biological research and has been widely used for chemical modification of proteins, constructing antibody-drug conjugates, enabling cell imaging studies. conjugation reactions with fast kinetics exquisite selectivity have under heavy pursuit they would allow clean protein just stoichiometric amounts reagents, which minimizes side reactions, simplifies purification broadens functional group tolerance. In this concept, we summarize the recent advances cysteine bioconjugation, discuss mechanism principles that underlie high efficiencies newly developed reactive reagents.

Language: Английский

Citations

35
I2-mediated coupling of quinazolinone enamines with 2-aminopyridines: a new strategy to access spiroquinazolinones DOI

Jingxi Fang,

Zhentao Pan, Tong Liu

et al.

Organic & Biomolecular Chemistry, Journal Year: 2023, Volume and Issue: 21(11), P. 2355 - 2360

Published: Jan. 1, 2023

Herein, we report a novel, rapid and efficient route to the spiroquinazolinone framework via an umpolung strategy mediated by molecular iodine. A library of functionalized iodide salts was synthesized in moderate good yields under ambient, metal-free mild conditions. The current methodology opens up new concise for construction spiroquinazolinones.

Language: Английский

Citations

14
DFT‐Guided Discovery of Ethynyl‐Triazolyl‐Phosphinates as Modular Electrophiles for Chemoselective Cysteine Bioconjugation and Profiling DOI Creative Commons
Christian E. Stieger, Y.H. Park, Mark A. R. de Geus

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(41)

Published: July 6, 2022

We report the density functional theory (DFT) guided discovery of ethynyl-triazolyl-phosphinates (ETPs) as a new class electrophilic warheads for cysteine selective bioconjugation. By using Cu

Language: Английский

Citations

19
Preparation of N-Aryl Amides by Epimerization-Free Umpolung Amide Synthesis DOI
Michael S. Crocker, Zihang Deng, Jeffrey N. Johnston

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(37), P. 16708 - 16714

Published: Sept. 6, 2022

Amide synthesis is one of the most widely practiced chemical reactions, owing to its use in drug development and peptide synthesis. Despite importance these applications, attendant effort eliminate waste associated with protocols has met limited success, pernicious α-epimerization often minimized but not eliminated when targeting challenging amides (e.g.,

Language: Английский

Citations

19
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
Umpolung‐Enabled Divergent Dearomative Carbonylations DOI
Ming‐Yang Wang, Wei‐Long Zeng,

Lin Chen

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(33)

Published: May 31, 2024

Although dearomative functionalizations enable the direct conversion of flat aromatics into precious three-dimensional architectures, case for simple arenes remains largely underdeveloped owing to high aromatic stabilization energy. We herein report a sequential addition two nucleophiles arene π-bonds through umpolung chromium-arene complexes. This mode enables divergent carbonylation reactions benzene derivatives by tolerating various in combination with alcohols or amines under CO-gas-free conditions, thus providing modular access functionalized esters amides. The tunable synthesis 1,3- 1,4-cyclohexadienes as well construction carbon quaternary centers further highlight versatility this dearomatization. Diverse late-stage modifications and derivatizations towards synthetically challenging bioactive molecules reveal synthetic utility. A possible mechanism was proposed based on control experiments intermediate tracking.

Language: Английский

Citations

4
Recent progress of chemical methods for lysine site-selective modification of peptides and proteins DOI
Jian Li, Jinjin Chen, Qi-Long Hu

et al.

Chinese Chemical Letters, Journal Year: 2024, Volume and Issue: unknown, P. 110126 - 110126

Published: June 1, 2024

Language: Английский

Citations

4
Peptide and Protein Cysteine Modification Enabled by Hydrosulfuration of Ynamide DOI Creative Commons
Changliu Wang, Zhenguang Zhao,

Reem Ghadir

et al.

ACS Central Science, Journal Year: 2024, Volume and Issue: 10(9), P. 1742 - 1754

Published: Aug. 21, 2024

Efficient functionalization of peptides and proteins has widespread applications in chemical biology drug discovery. However, the chemoselective site-selective modification remains a daunting task. Herein, highly efficient chemo-, regio-, stereoselective hydrosulfuration ynamide was identified as an method for precise by uniquely targeting thiol group cysteine (Cys) residues. This novel could be facilely operated aqueous buffer fully compatible with wide range proteins, including small model large full-length antibodies, without compromising their integrity functions. Importantly, this reaction provides Z-isomer corresponding conjugates exclusively superior stability, offering approach to peptide protein therapeutics. The potential application further exemplified Cys-bioconjugation variety ynamide-bearing functional molecules such molecule drugs, fluorescent/affinity tags, PEG polymers. It also proved redox proteomic analysis through Cys-alkenylation. Overall, study bioorthogonal tool Cys-specific functionalization, which will find broad synthesis peptide/protein conjugates.

Language: Английский

Citations

4