Dearomatization‐Rearomatization Reaction of Metal‐Polarized Aza‐ortho‐Quinone Methides DOI Open Access

Bao‐Cheng Wang,

Li Rao,

Kai‐Xin Fang

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(21)

Published: March 18, 2023

Abstract Metal‐polarized aza‐ ortho ‐quinone methides (aza‐ o ‐QMs) are a unique and efficient handle for azaheterocycle synthesis. Despite great achievements, the potential of these reactive intermediates has not yet been fully exploited, especially new reaction modes. Herein, we disclosed an unprecedented dearomatization process metal‐polarized ‐QMs, affording transient dearomatized spiroaziridine intermediates. Based on this serendipity, accomplished three sequential dearomatization‐rearomatization reactions benzimidazolines with aza‐sulfur ylides, enabling divergent synthesis bis‐nitrogen heterocycles high efficiency flexibility. Moreover, experimental theoretical studies were performed to explain proposed mechanisms observed selectivity. Further cellular evaluation dibenzodiazepine products identified hit compound antitumor drugs.

Language: Английский

Synthesis of Sulfilimines via Selective S–C Bond Formation in Water DOI
Yue Chen, Dongmei Fang,

He-sen Huang

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(12), P. 2134 - 2138

Published: March 20, 2023

Sulfilimines are valuable compounds both in organic synthesis and pharmaceuticals. Here we developed a mild simplified method for preparation of sulfilimines via selective S–C bond formation rather than traditional S–N formation. The is attractive useful the following reasons: it uses readily available alkylation reagent such alkyl bromide or iodide, water as solvent, easy to perform, convenient late-stage diversification drugs.

Language: Английский

Citations

45

Light-harvesting microelectronic devices for wireless electrosynthesis DOI
Bartosz Górski, Jonas Rein,

Samantha L. Norris

et al.

Nature, Journal Year: 2025, Volume and Issue: 637(8045), P. 354 - 361

Published: Jan. 8, 2025

Language: Английский

Citations

3

Ligand-Enabled Copper-Catalyzed Ullmann-Type S–C Bond Formation to Access Sulfilimines DOI

Xianda Wu,

Jiayi Zheng, Fu‐Sheng He

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 12, 2024

A copper-catalyzed Ullmann-type cross-coupling reaction of sulfenamides with aryl iodides is developed. The key to success the use a 2-methylnaphthalen-1-amine-derived amide ligand, which enables formation an S-C bond access functionalized sulfilimines in good excellent yields at room temperature. This method has advantages mild conditions, broad substrate scope, functional group compatibility, and high chemoselectivity. utility this protocol highlighted through late-stage modification drug-relevant molecules sulfilimine product derivatization.

Language: Английский

Citations

7

Biomolecule-Compatible Dehydrogenative Chan–Lam Coupling of Free Sulfilimines DOI
Tingting Meng, Lucille A. Wells, Tianxin Wang

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(27), P. 12476 - 12487

Published: June 29, 2022

Inspired by the discovery of a S═N bond in collagen IV network and its essential role stabilizing basement membranes, sulfilimines have drawn much attention fields chemistry biology. However, their further uptake is hindered lack mild, efficient, environmentally benign protocols which can be constructed under biomolecule-compatible conditions. Here, we report terminal oxidant-free copper-catalyzed dehydrogenative Chan–Lam coupling free diaryl with arylboronic acids excellent chemoselectivity broad substrate compatibility. The mild reaction conditions nature allow employment this protocol late-stage functionalization complex peptides, more importantly, as an effective bioconjugation method showcased model protein. A combined experimental computational mechanistic investigation reveals that inner-sphere electron-transfer process circumvents sacrificial oxidant employed traditional reactions. An energetically viable concerted pathway was located wherein copper hydride facilitates hydrogen-atom abstraction from isopropanol solvent to produce dihydrogen via four-membered transition state.

Language: Английский

Citations

29

Dearomatization‐Rearomatization Reaction of Metal‐Polarized Aza‐ortho‐Quinone Methides DOI Open Access

Bao‐Cheng Wang,

Li Rao,

Kai‐Xin Fang

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(21)

Published: March 18, 2023

Metal-polarized aza-ortho-quinone methides (aza-o-QMs) are a unique and efficient handle for azaheterocycle synthesis. Despite great achievements, the potential of these reactive intermediates has not yet been fully exploited, especially new reaction modes. Herein, we disclosed an unprecedented dearomatization process metal-polarized aza-o-QMs, affording transient dearomatized spiroaziridine intermediates. Based on this serendipity, accomplished three sequential dearomatization-rearomatization reactions benzimidazolines with aza-sulfur ylides, enabling divergent synthesis bis-nitrogen heterocycles high efficiency flexibility. Moreover, experimental theoretical studies were performed to explain proposed mechanisms observed selectivity. Further cellular evaluation dibenzodiazepine products identified hit compound antitumor drugs.

Language: Английский

Citations

12

Diphenylphosphinylhydroxylamine (DPPH) Affords Late‐Stage S‐imination to access free‐NH Sulfilimines and Sulfoximines DOI Creative Commons
Shanal Gunasekera, Alla Pryyma,

Jimin Jung

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(13)

Published: Jan. 30, 2024

Abstract Sulfilimines, as potential aza‐isosteres of sulfoxides, are valued building blocks, auxiliaries, ligands, bioconjugation handles, and precursors to versatile S(VI) scaffolds including sulfoximines sulfondiimines. Here, we report a thioether imination methodology that exploits O‐(diphenylphosphinyl)hydroxyl amine (DPPH). Under mild, metal‐free, biomolecule‐compatible conditions, DPPH enables late‐stage S‐imination on peptides, natural products, clinically trialled drug, shows both excellent chemoselectivity broad functional group tolerance. This methodological is extended an efficient high‐yielding one‐pot reaction for accessing free ‐NH with diverse substrates ones clinical importance. In the presence rhodium catalyst, sulfoxides S‐iminated in higher yields afford sulfoximines. was validated oxidatively delicate amatoxin give sulfilimine sulfoximine congeners. Interestingly, these new sulfoximine‐amatoxins show cytotoxicity. method further create sulfoximine‐Fulvestrant buthionine analogues.

Language: Английский

Citations

4

Yb(OTf)3-Catalyzed Formal (4 + 3) Cycloaddition Reactions of 3-Benzylideneindoline-2-thiones with Donor–Acceptor Cyclopropanes DOI
Yan Jiang, Haojie Ma, Xuelong Wang

et al.

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(20), P. 14587 - 14600

Published: Oct. 11, 2023

A Yb(OTf)3-catalyzed formal (4 + 3) cycloaddition reaction of donor-acceptor cyclopropanes with 3-benzylideneindoline-2-thiones as sulfur-containing 4π components has been successfully achieved. series functionalized 5,10-dihydro-2H-thiepino[2,3-b]indole derivatives were synthesized good yields and moderate to diastereoselectivity. The described herein represented the inaugural 3-benzylideneindoline-2-thiones.

Language: Английский

Citations

9

Intermolecular Sulfur Atom Transfer Cascade Enabled Late-Stage Introduction of Sulfilimines into Peptides DOI Creative Commons

Zeyuan He,

Yuyang Liu,

Guangjun Bao

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

A method of introducing sulfilimines fragment such as drugs, natural products, bioactive handles, and fluorescent tags into peptides at their acid sites was disclosed via an intermolecular sulfur atom transfer cascade reaction, both in the homogeneous phase and/or on-resins SPPS.

Language: Английский

Citations

3

A Sc(OTf)3-catalyzed one-pot two-step approach for spiro-oxindole dihydropyridine derivatives initiated by N-olefination of MBH carbonates DOI

Zhen-Hui Yan,

Run Lu,

Cheng Peng

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(9), P. 2294 - 2300

Published: Jan. 1, 2023

An efficient one-pot, two-step, three-component reaction of isatin-derived MBH carbonates, sulfilimines, and epoxides was achieved, thus affording pharmaceutically important spiro-oxindole dihydropyridines.

Language: Английский

Citations

8

Construction of Oxo-Bridged Diazocines via Rhodium-Catalyzed (4+3) Cycloaddition of Carbonyl Ylides with Azoalkenes DOI
Qiwen Pang, Jin Zhou, Yuling Wu

et al.

Organic Letters, Journal Year: 2022, Volume and Issue: 24(6), P. 1362 - 1366

Published: Feb. 4, 2022

Developing efficient strategies for synthesizing novel diazocine compounds is valuable because their use has been limited by synthetic accessibility. This work describes the catalytic (4+3) cycloaddition reaction of carbonyl ylides with azoalkenes generated in situ. The rhodium-catalyzed cascade features good atom and step economy, providing first access to oxo-bridged diazocines. product could be synthesized on a gram scale converted into diversely substituted dihydroisobenzofurans.

Language: Английский

Citations

12