Five-Membered Hetarene N-Oxides: Recent Advances in Synthesis and Reactivity

Five-membered heterocyclic N-oxides attracted special attention due to their strong application potential in medicinal chemistry and advanced materials science. In this regard, novel methods for their synthesis and functionalization are constantly required. In this short review, recent state-of-the-art achievements in the chemistry of isoxazoline N-oxides, 1,2,3-triazole 1-oxides and 1,2,5-oxadiazole 2-oxides are briefly summarized. Main routes to transition-metal-catalyzed and metal-free functionalization protocols along with mechanistic considerations are outlined. Transformation patterns of the hetarene N-oxide rings as precursors to other nitrogen heterocyclic systems are also presented.

Transition-Metal-Catalyzed Alkylation of Polyfluoroarenes through C–F Bond Cleavage

Synlett ◽

10.1055/a-1479-8264 ◽

2021 ◽

Author(s):

Tao Xiong ◽

Qian Zhang ◽

Qian Zhang

Keyword(s):

Transition Metal ◽

Medicinal Chemistry ◽

Materials Science ◽

Bond Cleavage ◽

Recent Advances ◽

Metal Catalyzed ◽

Site Selective

AbstractThe polyfluoroarenes are a subgroup of organofluorines that are widely utilized in both medicinal chemistry and materials science. We briefly summarize recent advances in the synthesis of these important compounds, with particular attention to our recent CuH-catalyzed defluorinative alkylation of polyfluoroarenes with alkenes in a highly site-selective C–F bond-cleavage fashion.1 Introduction2 Transition-Metal-Catalyzed Alkylation through Selective C–F Bond Cleavage3 CuH-Catalyzed Defluorinative Alkylation of Polyfluoroarenes with Alkenes4 Summary and Outlook

Recent Advances in the Synthesis of β-Ketonitriles

Synthesis ◽

10.1055/s-0036-1589128 ◽

2017 ◽

Vol 50 (03) ◽

pp. 485-498 ◽

Cited By ~ 8

Author(s):

Kensuke Kiyokawa ◽

Satoshi Minakata ◽

Takaya Nagata

Keyword(s):

Transition Metal ◽

Carbonyl Compounds ◽

Medicinal Chemistry ◽

Short Review ◽

Coupling Reactions ◽

Important Class ◽

The Past ◽

Recent Advances ◽

Ketone Enolates ◽

β-Ketonitriles are an important class of compounds in the field of organic and medicinal chemistry. Over the past decades, numerous efforts have been devoted to the development of new and efficient methodologies for the synthesis of these derivatives, and a number of efficient methods to accomplish this have been developed in recent years. In this context, this short review highlights recent advances in the synthesis of β-ketonitriles.1 Introduction2 Acylation of Alkyl Nitriles3 Electrophilic Cyanation of Ketone Enolates4 Electrophilic Cyanation of β-Keto Carbonyl Compounds5 Transition-Metal-Catalyzed Carbonylative Coupling Reactions6 Miscellaneous Examples7 Outlook

Recent Developments in the Synthesis of Pyrido[1,2-a]benzimidazoles

Synthesis ◽

10.1055/s-0036-1589533 ◽

2018 ◽

Vol 50 (11) ◽

pp. 2131-2149 ◽

Cited By ~ 7

Author(s):

Kamal Kapoor ◽

Parthasarathi Das ◽

Rajni Khajuria ◽

Sk. Rasheed ◽

Chhavi Khajuria

Keyword(s):

Transition Metal ◽

Medicinal Chemistry ◽

Type I ◽

Type Ii ◽

Aromatic Rings ◽

Metal Free ◽

Wide Range ◽

Recent Developments ◽

Metal Catalyzed ◽

Synthetic Approaches

Pyrido[1,2-a]benzimidazole is one of the most important azaheterocyclic compounds consisting of three fused aromatic rings. Molecules containing this core have displayed a wide range of applications in the field of medicinal chemistry. The synthesis of pyrido[1,2-a]benzimidazole and its derivatives has attracted organic chemists because of its tremendous utility in interdisciplinary branches of chemistry. In this context, this review discusses the main advances in the synthesis of pyrido[1,2-a]benzimidazoles via metal-mediated and metal-free reactions from 2000 to 2016.1 Introduction2 Synthetic Approaches to Pyrido[1,2-a]benzimidazoles2.1 Type I: Transition-Metal-Catalyzed Methods2.2 Type II: Metal-Free Approaches3 Conclusion

Formal nucleophilic borylation and borylative cyclization of organic halides

Organic & Biomolecular Chemistry ◽

10.1039/c6ob02369j ◽

2017 ◽

Vol 15 (2) ◽

pp. 285-300 ◽

Cited By ~ 51

Author(s):

K. Kubota ◽

H. Iwamoto ◽

H. Ito

Keyword(s):

Transition Metal ◽

Metal Free ◽

Recent Advances ◽

Organic Halides ◽

Recent advances in borylations of organic halides, including both transition-metal-catalyzed and metal-free methods are summarized. Borylative cyclization is also discussed.

Recent Advances in Amide Reductions

Synthesis ◽

10.1055/s-0036-1589144 ◽

2018 ◽

Vol 50 (05) ◽

pp. 984-997 ◽

Cited By ~ 27

Author(s):

Jérôme Blanchet ◽

Aurélien Chardon ◽

Eléonore Morisset ◽

Jacques Rouden

Keyword(s):

Scientific Community ◽

Short Review ◽

Metal Free ◽

Recent Advances ◽

This short review highlights recent advances in amide reductions. The last two years have witnessed important developments with milestones reached in catalytic hydrogenations and hydrosilylations. While metal-catalyzed processes still focus tremendous efforts from the scientific community, methodologies based on the metal-free hydrosilylation of amides have definitively joined the competition.1 Introduction2 Recent Use of Stoichiometric Reducing Reagents3 Hydrogenations4 Hydrosilylations5 Conclusion and Outlook

Transition metal-free C-3 functionalization of quinoxalin-2(1H)-ones: recent advances and sanguine future

New Journal of Chemistry ◽

10.1039/d1nj03445f ◽

2021 ◽

Author(s):

Kiran ◽

Payal Rani ◽

Sandhya Chahal ◽

Jayant Sindhu ◽

Sudhir Kumar ◽

...

Keyword(s):

Transition Metal ◽

Environmentally Benign ◽

Metal Free ◽

Gradual Shift ◽

Recent Advances ◽

A gradual shift from metal-catalyzed to metal-free methods is occurring, as the latter are more environmentally benign. This review discusses sustainable protocols for the construction of C–C, C–N, C–P, C–S, and C–O bonds via C–H functionalization of quinoxalin-2(1H)-ones.

Recent Advances in Direct C–H Functionalization of Pyrimidines

Synthesis ◽

10.1055/s-0036-1589520 ◽

2017 ◽

Vol 50 (02) ◽

pp. 193-210 ◽

Cited By ~ 20

Author(s):

Egor Verbitskiy ◽

Gennady Rusinov ◽

Oleg Chupakhin ◽

Valery Charushin

Keyword(s):

Transition Metal ◽

Pyrimidine Derivatives ◽

Metal Free ◽

Recent Advances ◽

Data spanning the period 2000–2017 on the direct C–H functionalization of pyrimidines are collected and discussed in this review. This demonstrates the surge of interest and creativity that this field of chemistry has experienced during the last two decades. Plausible applications of highly functionalized pyrimidines are also discussed.1 Introduction2 Transition-Metal-Catalyzed C–H Functionalization of Pyrimidine Derivatives3 Transition-Metal-Free Direct C–H Functionalization of Pyrimidine Derivatives4 Deprotonative Metalation of Pyrimidine Derivatives5 Conclusions

Recent Advances in Difluoromethylthiolation

Synthesis ◽

10.1055/s-0039-1690714 ◽

2019 ◽

Vol 52 (02) ◽

pp. 197-207 ◽

Cited By ~ 4

Author(s):

Xuan Xiao ◽

Zi-Tong Zheng ◽

Ting Li ◽

Jing-Lin Zheng ◽

Ting Tao ◽

...

Keyword(s):

Transition Metal ◽

Short Review ◽

Recent Advances ◽

Metal Catalyzed ◽

Sulfur Containing

The difluoromethylthio group (HCF2S), which has been identified as a valuable functionality in drug and agrochemical discovery, has received increased attention recently. Two strategies, difluoromethylation and direct difluoromethylthiolation, have been well established for HCF2S incorporation. The former strategy suffers from the need to prepare sulfur-containing substrates. In contrast, direct difluoromethylthiolation is straightforward and step-economic. This short review covers the recent advances in direct difluoromethylthiolation, including electrophilic, radical, and transition-metal-catalyzed or -promoted reactions.1 Introduction2 Electrophilic Difluoromethylthiolation3 Radical Difluoromethylthiolation4 Transition-Metal-Catalyzed or -Promoted Difluoromethylthiolation5 Conclusions and Perspectives

Recent advances in the functionalization of polyfluoro(aza)aromatics via C–C coupling strategies

Organic & Biomolecular Chemistry ◽

10.1039/d1ob00472g ◽

2021 ◽

Author(s):

Timofey D. Moseev ◽

Mikhail V. Varaksin ◽

Denis A. Gorlov ◽

Valery N. Charushin ◽

Oleg N. Chupakhin

Keyword(s):

Transition Metal ◽

Coupling Reactions ◽

Metal Free ◽

Recent Advances ◽

Metal Catalyzed ◽

Coupling Strategies

This review highlights the recent advances in the functionalization of polyfluoro(aza)aromatics via both transition metal-catalyzed and metal-free C–C coupling reactions for the period from 2006 to the beginning of 2021.

Recent Advances in the Addition of Amide/Sulfonamide Bonds to Alkynes

Molecules ◽

10.3390/molecules24010164 ◽

2019 ◽

Vol 24 (1) ◽

pp. 164 ◽

Cited By ~ 1

Author(s):

Fei Zhao ◽

Pinyi Li ◽

Xiaoyan Liu ◽

Xiuwen Jia ◽

Jiang Wang ◽

...

Keyword(s):

Transition Metal ◽

Present Review ◽

Reaction Conditions ◽

Metal Free ◽

Triple Bonds ◽

Recent Advances ◽

Direct Functionalization ◽

The addition of amide/sulfonamide bonds to alkynes is not only one of the most important strategies for the direct functionalization of carbon–carbon triple bonds, but also a powerful tool for the downstream transformations of amides/sulfonamides. The present review provides a comprehensive summary of amide/sulfonamide bond addition to alkynes, including direct and metal-free aminoacylation, based-promoted aminoacylation, transition-metal-catalyzed aminoacylation, organocatalytic aminoacylation and transition-metal-catalyzed aminosulfonylation of alkynes up to December 2018. The reaction conditions, regio- and stereoselectivities, and mechanisms are discussed and summarized in detail.