Ruthenium‐Catalyzed C−C Bond Cleavage of 2<i>H</i>‐Azirines: A Formal [3+2+2] Cycloaddition to Fused Azepine Skeletons

Li, Tengfei; Xu, Fen; Li, Xincheng; Wang, Chunxiang; Wan, Boshun

doi:10.1002/anie.201510820

Cited by 98 publications

(27 citation statements)

References 142 publications

(37 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Our investigation showed that, upon sulfonylation of the oximes, only N ‐aryl carboxamidoximes ( 1 ) can undergo the intramolecular electrophilic aromatic substitution reaction to form the corresponding CN bond. In the absence of the amide nitrogen and the lack of a strong base in the reaction, heterolytic NO bond cleavage of ketoximes 4–6 predominantly triggered the subsequent CC bond dissociation between the oxime carbon and the neighborintg carbons to undergo Beckmann rearrangement or fragmentation reactions. We postulated that the amide nitrogen provided a resonance stabilization for the putative nitrene species formed after the heterolytic cleavage of the NO bond and allowed the electrophilic nitrogen to be captured by the N ‐aryl ring carbon.…”

Section: Methodsmentioning

confidence: 99%

Investigation of O‐Sulfonylation‐promoted Heterolytic NO Bond Cleavage of Amidoximes and Ketoximes

Hsieh

Liao

Liu

et al. 2017

J Chinese Chemical Soc

View full text Add to dashboard Cite

Two different reaction pathways were observed in the sulfonylation of N-phenylbenzamidoximes. The reaction with o-NsCl at a heating temperature gave N,N 0 -diphenylureas via Tiemann rearrangement, while the reaction with Ts 2 O at a lower temperature formed 2-phenylbenzimidazoles via intramolecular electrophilic aromatic substitution. When the amide nitrogen was replaced with carbon substituents, oxime derivatives of benzoins and benzils underwent Beckmann fragmentation reactions upon sulfonylation, whereas sulfonylation of 2-phenylacetophenone oxime afforded exclusively the Beckmann rearrangement adduct.

show abstract

Section: Methodsmentioning

confidence: 99%

Investigation of O‐Sulfonylation‐promoted Heterolytic NO Bond Cleavage of Amidoximes and Ketoximes

Hsieh

Liao

Liu

et al. 2017

J Chinese Chemical Soc

View full text Add to dashboard Cite

show abstract

“…Wang, Wan, and co-workers reported a Ru-catalyzed [3+2+2]cycloaddition reaction of 2H-azirines with diynes leading to fused azepine skeletons (Scheme 13). 11 This transformation provides a facile and straightforward method for the formation of fused azepine derivatives, and features broad substrate scope and a wide range of functional groups. Notably, the C-C bond of the 2H-azirines was selective cleaved to achieve the tandem [5+2]-cycloaddition reaction.…”

Section: [3+2+2] Cycloadditionmentioning

confidence: 99%

Recent Advances in Cycloaddition Reactions with Alkynes to Construct Heterocycles

Qin

2020

Synthesis

View full text Add to dashboard Cite

Heterocyclic compounds, especially N-heterocycles and O-heterocycles, are prominent structural motifs present in numerous natural products and medically and/or economically important compounds. This review aims to describe the development of transition-metal-catalyzed cycloaddition reactions of functionalized m-atom partners with alkynes to access a wide range of five-, six-, and seven-membered heterocycles, that is functionalized N-heterocycles and O-heterocycles such as azepines, isoquinolines, isocoumarins, spiroheterocycles, indoles, furans, and pyrroles, in a selectively controlled manner with an emphasis on scope and limitations and with a discussion of the mechanisms.1 Introduction2 Intermolecular Cycloaddition To Construct Azepine Derivatives2.1 [5+2] Cycloaddition2.2 [3+2+2] Cycloaddition2.3 [3+2]/[5+2] Cycloaddition3 Intermolecular [4+2] Cycloaddition To Construct Isoquinolines or Isocoumarins4 Intermolecular [3+2] Cycloaddition To Construct Spiroheterocyclic Compounds, Indoles, Furans, and Pyrroles5 Summary and Outlook

show abstract

“…The first report involving 2 H ‐azirines as 3π‐component in [3+2+2] cycloadditions is reported by Tengfei Li and co‐workers. It involves the ruthenium‐catalyzed [3+2+2] cycloaddition of diynes with 2 H ‐azirines under mild reaction conditions to construct seven‐membered fused azepine derivatives (Scheme , Figure ) …”

Section: Ruthenium‐catalyzed [3+2+2] Cycloaddition Reactions Of Azmentioning

confidence: 99%

Transition‐Metal‐Catalyzed [3+2+2] Cycloaddition Reactions

et al. 2017

View full text Add to dashboard Cite

[3+2+2] Cycloaddition reactions are of key importance in organic chemistry for the synthesis of seven‐membered mono‐ and condensed carbocycles. This review article summarises the different reports on transition‐metal‐catalysed [3+2+2] cycloaddition reactions since 2000. Different transition‐metals, such as Ni, Rh, Pd, Co, or Ru, which have been earlier reported for higher order [3+2+2] cycloaddition reactions are summarized in this article. The [3+2+2] cycloadditions of different functionalized substrates afford cycloheptane derivatives, 6–7,5–7 condensed bicyclic carbocycles, or 5–7–5 or 6–7–5 condensed tricyclic carbocycles. These higher order cycloaddition reactions may provide an easy route for the total synthesis of natural products, or as a preferable key synthetic step leading to final structure.

show abstract

Ruthenium‐Catalyzed C−C Bond Cleavage of 2H‐Azirines: A Formal [3+2+2] Cycloaddition to Fused Azepine Skeletons

Cited by 98 publications

References 142 publications

Investigation of O‐Sulfonylation‐promoted Heterolytic NO Bond Cleavage of Amidoximes and Ketoximes

Investigation of O‐Sulfonylation‐promoted Heterolytic NO Bond Cleavage of Amidoximes and Ketoximes

Recent Advances in Cycloaddition Reactions with Alkynes to Construct Heterocycles

Transition‐Metal‐Catalyzed [3+2+2] Cycloaddition Reactions

Contact Info

Product

Resources

About