DMF as a Source of Oxygen and Aminomethine: Stereoselective 1,2-Insertion of Rhodium(II) Azavinyl Carbenes into the C═O Bond of Formamides for the Synthesis of <i>cis</i>-Diamino Enones

Jung, Da Jung; Jeon, Hyun Ji; Kim, Ju Hyun; Kim, Youngmee; Lee, Sang Gi

doi:10.1021/ol500723s

Cited by 83 publications

(14 citation statements)

References 47 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[37] Te rtiary benzamides 125 were chosen as the reaction partner.T he reaction was proposed to first produce unstable4 -oxazoline 128 via carbonyl ylide 127, before ring-opening of 128 affords azomethine ylide 129,f ollowed by ar ing contraction to give 130.S ubsequent ringopeningo f130 affords zwitterionic intermediate 131,w hich forms enaminone 126 through proton rearrangement.Avariety of benzamides and triazoles were toleratedi nt his reaction. Similar transformationsw ere reported by the groups of Lee [38] and Murakami, [39] in which DMF was used instead of benzamide. Similar transformationsw ere reported by the groups of Lee [38] and Murakami, [39] in which DMF was used instead of benzamide.…”

Section: Attack By Oxygen Atomsupporting

confidence: 60%

See 1 more Smart Citation

Recent Advances in the Synthesis of Heterocycles and Related Substances Based on α‐Imino Rhodium Carbene Complexes Derived from N‐Sulfonyl‐1,2,3‐triazoles

Jiang

Sun

Tang

et al. 2016

Chemistry A European J

200

View full text Add to dashboard Cite

In recent years, α-imino rhodium carbene complexes derived by ring-opening of N-sulfonyl-1,2,3-triazoles have attracted much attention from organic chemists. Many transformations of these species have been reported that involve, in most cases, nucleophilic attack at the carbene center of the α-imino rhodium carbene, facilitating the synthesis of a wide range of novel and useful compounds, particularly heterocycles. This Minireview mainly focuses on advances in the transformation of N-sulfonyl-1,2,3-triazoles during the past two years.

show abstract

Section: Attack By Oxygen Atomsupporting

confidence: 60%

“…Notably, when N , N ‐dimethylacetamide was used instead of tertiary benzamide, the corresponding adduct was not produced. Similar transformations were reported by the groups of Lee and Murakami, in which DMF was used instead of benzamide.…”

Section: Reactions Of N‐sulfonyl‐123‐triazolesmentioning

confidence: 99%

Recent Advances in the Synthesis of Heterocycles and Related Substances Based on α‐Imino Rhodium Carbene Complexes Derived from N‐Sulfonyl‐1,2,3‐triazoles

Jiang

Sun

Tang

et al. 2016

Chemistry A European J

200

View full text Add to dashboard Cite

show abstract

“…In addition, α‐imino metal carbenes can react with electrophiles because the nitrogen atom of the α‐imino group is inherently nucleophilic. Accordingly, these amphiphilic α‐imino metal carbenes smoothly react with nitriles,5 alkynes,6 allenes,7 isocyanates and isothiocyanates,8 furans,9 aldehydes and imines,10 α,β‐unsaturated aldehydes,11 indoles,12 arenes,13 alkenes,6d, 14 and amides15 to afford a multitude of heterocycles 16…”

Section: Methodsmentioning

confidence: 99%

Aza‐[4+3] and Aza‐[3+2] Annulations for Synthesis of Dihydroazepines and Dihydropyrroles from Alkynes, Sulfonyl Azides, and 1,3‐Dienes

Kim

et al. 2014

Asian J Org Chem

View full text Add to dashboard Cite

We report aza-[4+3] annulation through sequential [3+2]-[2+1] cycloadditions-aza-Cope rearrangement for the synthesis of dihydroazepines. Aza-[3+2] annulation was achieved through [3+2]-[2+1]-aza-Cope rearrangement-1,3migration or [3+2]-[2+1]-Clock rearrangement, leading to the formation of dihydropyrroles. In addition, dihydroazepines thermally 1,3-migrated to give dihydropyrroles. This method affords a straightforward synthetic pathway from simple triazoles to produce dihydroazepines and dihydropyrroles together with N 2 as the single byproduct. This procedure can be successfully applied to a one-pot process starting from terminal alkynes, azides, and dienes.Azaheterocycles are a highly important class of compounds due to their biological activities and pharmaceutical applications. [1] In particular, dihydroazepines, dihydropyrroles, and pyrroles are constituents of a valuable privileged structure in organic chemistry. [2] For this reason, the development of efficient synthetic methods for producing multisubstituted azaheterocyclic compounds from simple and easily accessible starting materials has been continuously required. [3] Now, we report an efficient aza-[4+3] annulation and aza-[3+2] annulation starting from terminal alkynes, sulfonyl azides, and 1,3-dienes in one-pot (Scheme 1).Recently, 1-sulfonyl-1,2,3-triazoles, which are easily prepared from copper-catalyzed 1,3-dipolar cycloaddition of terminal alkynes with sulfonyl azides, have been extensively investigated as precursors of a-imino metal carbenes. [4] The high reactivity of a-imino metal carbenes toward nucleophiles is caused by the intrinsically electrophilic properties of the metal carbene species. In addition, a-imino metal carbenes can react with electrophiles because the nitrogen atom of the a-imino group is inherently nucleophilic. Accordingly, these amphiphilic a-imino metal carbenes smoothly react with nitriles, [5]

show abstract

“…Rhodium-stabilized donor/acceptor carbenes as reactive intermediates have been widely applied in modern organic synthesis [14][15][16][17][18][19][20][21][22][23][24][25][26]. Among them, N-sulfonyl-1,2,3-triazole as an alternative source of carbene precursor has been used to achieve the transannulation reaction for the direct synthesis of heterocycles [27][28][29][30][31][32][33][34][35][36][37][38][39][40][41].…”

Section: Introductionmentioning

confidence: 99%

Rhodium (II)-Catalyzed Synthesis of Tetracyclic 3,4-Fused Indoles and Dihydroindoles

et al. 2020

View full text Add to dashboard Cite

show abstract

DMF as a Source of Oxygen and Aminomethine: Stereoselective 1,2-Insertion of Rhodium(II) Azavinyl Carbenes into the C═O Bond of Formamides for the Synthesis of cis-Diamino Enones

Cited by 83 publications

References 47 publications

Recent Advances in the Synthesis of Heterocycles and Related Substances Based on α‐Imino Rhodium Carbene Complexes Derived from N‐Sulfonyl‐1,2,3‐triazoles

Recent Advances in the Synthesis of Heterocycles and Related Substances Based on α‐Imino Rhodium Carbene Complexes Derived from N‐Sulfonyl‐1,2,3‐triazoles

Aza‐[4+3] and Aza‐[3+2] Annulations for Synthesis of Dihydroazepines and Dihydropyrroles from Alkynes, Sulfonyl Azides, and 1,3‐Dienes

Rhodium (II)-Catalyzed Synthesis of Tetracyclic 3,4-Fused Indoles and Dihydroindoles

Contact Info

Product

Resources

About