Fe‐Catalyzed Aliphatic C−H Methylation of Glycine Derivatives and Peptides DOI

Silin Song,

Xiuliang Cheng,

Shiyan Cheng

et al.

Chemistry - A European Journal, Journal Year: 2022, Volume and Issue: 29(17)

Published: Dec. 22, 2022

Direct and selective C-H methylation is a powerful tool with which to install methyl groups into organic molecules, particularly useful in pharmaceutical chemistry. However, practical methods for such modification of biologically interesting targets have been rarely developed. We here report an iron-catalyzed C(sp3 )-H reaction glycine derivatives, peptides drug-like molecules alcohol the presence di-tert-butyl peroxide. A readily available iron catalyst plays multiple roles transformation, accelerates oxidation C-N bonds C=N double bonds, activates imine intermediates as Lewis acids by bidentate chelation, at same time facilitates cleavage peroxide generate radicals. variety methylated N-aryl derivatives were obtained good yield excellent chemo- site-selectivity. This scalable, easily managed, can be completed within 1-2 h. It features economic, bio-friendly catalyst, green solvent low toxic reagents, will provide effective access precise biomolecules natural products.

Language: Английский

Recent Progress in Synthetic Applications of Hypervalent Iodine(III) Reagents DOI Creative Commons
Akira Yoshimura, Viktor V. Zhdankin

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

Published: Sept. 13, 2024

Hypervalent iodine(III) compounds have found wide application in modern organic chemistry as environmentally friendly reagents and catalysts. iodine are commonly used synthetically important halogenations, oxidations, aminations, heterocyclizations, various oxidative functionalizations of substrates. Iodonium salts arylating reagents, while iodonium ylides imides excellent carbene nitrene precursors. Various derivatives benziodoxoles, such azidobenziodoxoles, trifluoromethylbenziodoxoles, alkynylbenziodoxoles, alkenylbenziodoxoles group transfer the presence transition metal catalysts, under metal-free conditions, or using photocatalysts photoirradiation conditions. Development hypervalent catalytic systems discovery highly enantioselective reactions chiral represent a particularly recent achievement field chemistry. Chemical transformations promoted by many cases unique cannot be performed any other common, non-iodine-based reagent. This review covers literature published mainly last 7-8 years, between 2016 2024.

Language: Английский

Citations

28
Recent progress in the application of iodonium ylides in organic synthesis DOI
Xia Mi, Chao Pi, Weisheng Feng

et al.

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(24), P. 6999 - 7015

Published: Jan. 1, 2022

This review summarizes the recent advances in synthetic application of iodonium ylides covering 2017 to 2022.

Language: Английский

Citations

39
Three-component synthesis ofN-naphthyl pyrazolesviaRh(iii)-catalyzed cascade pyrazole annulation and Satoh–Miura benzannulation DOI

Demao Chen,

Liyun Zhou,

Yunyun Liu

et al.

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(27), P. 4036 - 4039

Published: Jan. 1, 2023

The synthesis of N-naphthyl pyrazoles has been realized by the direct three-component reactions enaminones, aryl hydrazine hydrochlorides and internal alkynes via Rh(III) catalysis. synthetic employing simple substrates lead to simultaneous construction dual cyclic moieties, including a pyrazole ring phenyl ring, sequential formation two C-N three C-C bonds.

Language: Английский

Citations

33
Condition-Controlled Selective Synthesis of Pyranone-Tethered Indazoles or Carbazoles through the Cascade Reactions of N-Nitrosoanilines with Iodonium Ylides DOI
Kelin Wang,

Xia Song,

Yongdi Xin

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(24), P. 4422 - 4428

Published: June 8, 2023

Presented herein is a condition-controlled selective synthesis of pyranone-tethered indazoles or carbazole derivatives via the cascade reactions N-nitrosoanilines with iodonium ylides. Mechanistically, formation former involves an unprecedented process including nitroso group-directed C(sp2)–H bond alkylation N-nitrosoaniline ylide followed by intramolecular C-nucleophilic addition to moiety, solvent-assisted cyclohexanedione ring opening, and transesterification/annulation. On contrary, latter initial annulation denitrosation. These developed protocols feature easily controllable selectivity, mild reaction conditions, clean sustainable oxidant (air), valuable products that are structurally diverse. In addition, utility was showcased their facile diverse transformations into synthetically biologically interesting compounds.

Language: Английский

Citations

26
Ru(II)-Catalyzed Decarbonylative Alkylation and Annulations of Benzaldehydes with Iodonium Ylides under Chelation Assistance DOI
Xiang Li, Yang Shen, Guodong Zhang

et al.

Organic Letters, Journal Year: 2022, Volume and Issue: 24(29), P. 5281 - 5286

Published: July 18, 2022

A Ru(II)-catalyzed decarbonylative alkylation and annulation of salicylaldehydes 2-aminobenzaldehydes with iodonium ylides has been developed for the synthesis dibenzo[b,d]furans NH-free carbazolones. The reaction proceeds smoothly under mild conditions a low catalyst loading broad substrate compatibility. Notably, hydroxy free amino groups were demonstrated to be effective directing groups, enabling successful aldehyde C–H bond activation subsequent decarbonylation inexpensive Ru(II) catalyst.

Language: Английский

Citations

29
Rhodium(III)‐Catalyzed Divergent C−H Functionalization of N‐Aryl Amidines with Iodonium Ylides: Access to Carbazolones and Zwitterionic Salts DOI
Jie Ren, Yang Liu, Chao Pi

et al.

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(11), P. 1817 - 1823

Published: Feb. 7, 2023

Abstract We described an Rhodium(III)‐catalyzed divergent C−H bond functionalization of N ‐aryl amidines with iodonium ylides. Carbazolones and zwitterionic salts were diversely constructed through intermolecular annulation intramolecular proton transfer under the different reaction conditions. This protocol is operationally simple tolerates a variety functional groups. The efficient post‐modification pharmaceutical molecules demonstrates its practicability.

Language: Английский

Citations

19
Accessing 7,8-Dihydroquinoline-2,5-diones via Rh-Catalyzed Olefinic C–H Activation/[4+2] Cyclization DOI
Xueqing Liu,

Sijia Shi,

Wenqian Ding

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(24), P. 5136 - 5140

Published: June 7, 2024

Herein, we report a rhodium-catalyzed C–H activation/[4+2] cyclization reaction between α,β-unsaturated amides and iodonium ylides for the synthesis of novel 7,8-dihydroquinoline-2,5-diones analogues. This protocol provides series pyridones fused with saturated cycles good functional group compatibility, water air tolerance, to excellent yields under mild green conditions. Additionally, scale-up can be smoothly performed as low 0.25 mol % catalyst loading. Recycling experiments different transformation were also carried out demonstrate potential synthetic utility this protocol.

Language: Английский

Citations

8
Application of Sulfoxonium Ylides or Iodonium Ylides in Rhodium‐Catalyzed Synthesis of Phenanthrenes DOI
Xiao Liu, Bingxin Zhou, Kelu Yan

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(8), P. 1744 - 1750

Published: Feb. 22, 2024

Abstract The transmetalation triggered rhodium‐catalyzed C−H bond activation and tandem annulation of 2‐biphenylboronic acids with sulfoxonium ylides or iodonium has been developed. Various products phenanthrenes were constructed under redox‐neutral conditions in 34–86% yields. Several mechanism exploration experiments derivatization reactions conducted sequence to gain a deeper understanding the process potential this transformation. It offers an alternative approach for synthesis phenanthrene derivatives.

Language: Английский

Citations

6
Iodonium ylides: an emerging and alternative carbene precursor for C–H functionalizations DOI
Sanjeev Kumar, Vaishnavi Borkar,

Mohd Mujahid

et al.

Organic & Biomolecular Chemistry, Journal Year: 2022, Volume and Issue: 21(1), P. 24 - 38

Published: Nov. 23, 2022

The metal-catalyzed successive activation and functionalization of arene/heteroarene is one the most fundamental transformations in organic synthesis leads to privileged scaffolds natural products, pharmaceuticals, agrochemicals, fine chemicals. Particularly, transition-metal-catalyzed C-H arenes with carbene precursors via metal migratory insertion has been well studied. As a result, diverse have evaluated, such as diazo compounds, sulfoxonium ylides, triazoles, etc. In addition, there significant developments use iodonium ylides recent years, these reactions proceed high efficiencies selectivities. This review provides comprehensive overview functionalizations, including scope, limitations, their potential synthetic applications.

Language: Английский

Citations

27
Rh(iii)-catalyzed C–H/C–C bond annulation of enaminones with iodonium ylides to form isocoumarins DOI
Zi Yang,

Chaoshui Liu,

Jieni Lei

et al.

Chemical Communications, Journal Year: 2022, Volume and Issue: 58(97), P. 13483 - 13486

Published: Jan. 1, 2022

A straightforward approach to synthesise isocoumarins via Rh(III)-catalyzed C-H/C-C bond activation/annulation cascade of enaminones and iodonium ylides has been explored. The established protocol is characterized by an exceedingly simple reaction system, high regioselectivity good functional group tolerance. Moreover, this strategy may provide a new route cleavage the C(sp2)-C(O) unstrained ketones.

Language: Английский

Citations

24