Synthesis of Pyrroles from Terminal Alkynes, <i>N</i>-Sulfonyl Azides, and Alkenyl Alkyl Ethers through 1-Sulfonyl-1,2,3-triazoles

Kim, Cheol-Eui; Park, Sangjune; Eom, Dahan; Seo, Boram; Lee, Phil Ho

doi:10.1021/ol500718s

Cited by 126 publications

(26 citation statements)

References 48 publications

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“…More recently, we have reported that the reaction of triazoles with alkenyl alkyl ethers give rise to pyrroles through the corresponding dihydropyrroles 17. Next, we were interested in whether 1,3‐dienes can act as dipolarophiles to construct a dihydroazepine and dihydropyrrole scaffold 18…”

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

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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]

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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

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“…Alternatively,i np ath b, the alkene undergoes cyclopropanation to give intermediates 8,f ollowedb yr ing enlargement to furnish the corresponding dihydropyrroles 7.F urthermore, Lee and co-workersa lso extended the methodology into at hreecomponent, one-pot procedure starting from the tosyl azide, terminal alkyne, and alkenyl alkyl ether. [10] Shortly thereafter,Liand co-workersreported asimilar rhodium-catalyzed reaction of N-sulfonyl-1,2,3-triazoles 1 with ketene silyl acetal to form 3,4-disubstituted 3-pyrrolin-2-ones 10 (Scheme 4). [12] The products were afforded in high yields when alkyl ketene silyl acetals (R 2 = alkyl) were employed.…”

Section: Attack By Carbon Atommentioning

confidence: 99%

“…In early 2014, the groups of Lee and Anbarasan independently reported rhodium‐catalyzed transannulations of N ‐sulfonyl‐1,2,3‐triazoles 1 with vinyl ethers to synthesize various polysubstituted pyrroles 5 (Scheme ). The reaction scope was broad, and various triazoles and alkenyl alkyl ethers could participate in the reaction.…”

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

212

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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.

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“…Synthesis of pyrroles through a three component coupling of alkynes, sulfonyl azides, and enol ethers using a dual copper rhodium catalyst system proceeds through copper-catalyzed formation of the triazole followed by rhodium-catalyzed formation of the carbene complex and net [3+2] cycloaddition with the enol ether accompanied by alcohol elimination [1119]. The dual copper rhodium system was used to prepare α-amino silyl enol ethers from terminal alkynes, tosyl azide, and hydroxysilanes [1120].…”

Section: Page 129 Of 218mentioning

confidence: 99%

The chemistry of the carbon-transition metal double and triple bond: Annual survey covering the year 2014

Herndon

2016

Coordination Chemistry Reviews

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Synthesis of Pyrroles from Terminal Alkynes, N-Sulfonyl Azides, and Alkenyl Alkyl Ethers through 1-Sulfonyl-1,2,3-triazoles

Cited by 126 publications

References 48 publications

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

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

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

The chemistry of the carbon-transition metal double and triple bond: Annual survey covering the year 2014

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