Rhodium(II)-Catalyzed Stereocontrolled Synthesis of Dihydrofuran-3-imines from 1-Tosyl-1,2,3-triazoles

Boyer, Alistair

doi:10.1021/ol500309x

Cited by 89 publications

(25 citation statements)

References 65 publications

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“…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

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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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“…Fokin further expanded the rearrangement concept to sulfonyl triazoles 138 bearing either a tertiary or quaternary center at C-4 to furnish dienes 141 (Scheme 31). 50 Cycloalkyl and tert-alkyl triazoles provided the expected hydride and alkyl shift, respectively, whereas protection of an alcohol as an acetoxy led to the exclusive migration of the acetoxy group furnishing acetyl enols in excellent yields. More interestingly, a piperazine triazole led to a selective migration of the amino group to provide the corresponding imine enamine in good yield.…”

Section: Stereoselective Arylationmentioning

confidence: 97%

“…Boyer reported the rhodium(II)-catalyzed transformation of 4,5-and 5-substituted N-sulfonyl triazoles bearing allyl and propargylic ethers into dihydrofuran-3-imines. 50 Lee reported an extension of the formal 3+2 cycloaddition of electron rich olefins to alkenyl ethers to afforded substituted pyrroles after the elimination of ethoxide. 51 Following up on Fokin's formal 1,3-insertion chemistry, Lee reported the synthesis of cis-diamino enones from N,N-dialkylsubstituted formamides.…”

Section: Stereoselective Arylationmentioning

confidence: 99%

Reactions of metallocarbenes derived from N-sulfonyl-1,2,3-triazoles

2014

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Metal-stabilized carbenes derived from diazo compounds have become broadly useful reactive intermediates for organic synthesis. This tutorial review will describe the recent advances in using N-sulfonyl-1,2,3-triazoles as precursors for the formation of metal-bound imino carbene intermediates. These intermediates undergo a variety of synthetically useful transformations, which include transannulation reactions to generate new heterocycles, cyclopropanation and subsequent ring expansions, ylide formation with subsequent rearrangements, and C-H functionalization. Furthermore, many of these transformations can be conducted with high levels of enantioselectivity by use of chiral rhodium(II) catalysts.

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“…1029) followed by rearrangement was proposed based on the isolation of a cyclopropylimine from some substrates. Tetrahydrofuran imines were synthesized through reaction of sulfonated triazoles containing allylic ethers with rhodium catalysts in a process that involves carbene complex formation, followed by intramolecular ylide formation, followed by [2,3] sigmatropic rearrangement [1099]. A mechanistically similar approach to the synthesis of related oxygen and sulfur heterocycles was also reported [1100].…”

Section: Scheme 80 Reaction Of Heteroarylcarbene Complexes Through Cmentioning

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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Rhodium(II)-Catalyzed Stereocontrolled Synthesis of Dihydrofuran-3-imines from 1-Tosyl-1,2,3-triazoles

Cited by 89 publications

References 65 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

Reactions of metallocarbenes 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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