Gold-Catalyzed Domino Aminocyclization/1,3-Sulfonyl Migration of N-Substituted <i>N</i>-Sulfonyl-aminobut-3-yn-2-ols to 1-Substituted 3-Sulfonyl-1<i>H</i>-pyrroles

Teo, Wan Teng; Rao, Weidong; Koh, Ming Joo; Chan, Philip Wai Hong

doi:10.1021/jo401083m

Cited by 56 publications

(22 citation statements)

References 57 publications

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“…Subsequently, Chan’s group presented a gold-catalyzed domino aminocyclization/1,3-sulfonyl migration of N -substituted N -sulfonyl-aminobut-3-yn-2-ols 111 to synthesize highly functional pyrroles 112 (Scheme 35) [49]. A screening of gold catalysts disclosed that the NHC ( N -heterocyclic carbene)-gold(I) complex 113 was found to be the most effective catalyst for this intramolecular aminosulfonylation of alkynes.…”

Section: Transition-metal-catalyzed Addition Of Sulfonamide Bonds mentioning

confidence: 99%

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

Zhao

Liu

et al. 2019

Molecules

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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.

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Section: Transition-metal-catalyzed Addition Of Sulfonamide Bonds mentioning

confidence: 99%

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

Zhao

Liu

et al. 2019

Molecules

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“…Initially, the α-position of sulfonyl group would undergo lithiation upon treatment with LDA to deliver A and then a 4-exo-dig cyclization would occur to generate four-membered β-sultam intermediate B 63 , 64 , 67 , 68 . Subsequently, B presumably undergoes a 1,3-sulfonyl migration to form lithium thiete sulfone intermediate C 69 , 70 , which could be protonated by MeOH to deliver product 2 . When MeOH was replaced by other electrophilic reagents, intermediate C could be functionalized directly to obtain N -substituted thiete sulfone products.…”

Section: Resultsmentioning

confidence: 99%

Skeletal reorganization divergence of N-sulfonyl ynamides

Zeng

Lin

et al. 2020

Nat Commun

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Skeletal reorganization is a type of intriguing processes because of their interesting mechanism, high atom-economy and synthetic versatility. Herein, we describe an unusual, divergent skeletal reorganization of N-sulfonyl ynamides. Upon treatment with lithium diisopropylamine (LDA), N-sulfonyl ynamides undergo a skeletal reorganization to deliver thiete sulfones, while the additional use of 1,3-dimethyl-tetrahydropyrimidin-2(1H)-one (DMPU) shifts the process to furnish propargyl sulfonamides. This skeletal reorganization divergence features broad substrate scope and scalability. Mechanistically, experimental and computational studies reveal that these processes may initiate from a lithiation/4-exo-dig cyclization cascade, and the following ligand-dependent 1,3-sulfonyl migration or β-elimination would control the chemodivergence. This protocol additionally provides a facile access to a variety of privileged molecules from easily accessible ynamides.

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“…A cross‐over experiment demonstrated that the migration proceeds intramolecularly. This was further witnessed by the lack of reaction of a 3‐unsubstituted pyrrole (no SO 2 R 5 ) with TsCl in the presence of the same catalyst 39…”

Section: N‐nucleophilesmentioning

confidence: 99%

Homogeneous Gold‐Catalyzed Cyclization Reactions of Alkynes with N‐ and S‐Nucleophiles

et al. 2015

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This review covers the formation of N-a nd S-containing heterocycles,i nitiated by gold-catalyzed nucleophilic attack of N-o rS-nucleophiles ontoa lkynes. These typeso fn ucleophiles have been somewhat overlooked as compared to their C-o rO-counterparts in other reviews.I nt his particularw ork, their intramolecular gold-mediated attack ontoa lkynesi sr eviewedi nd epth.I ti ss tructured in such af ashion that the reader will get ac learv iew of which substrates react in which cyclization mode. 1I ntroduction 2N-Nucleophiles 2.Scheme1.endo-a nd exo-dig cyclization modes for heteroatom attack onto Au-activated triple bonds. REVIEWSWouter Debrouwer et al. Scheme 2. Au(I)-catalyzed formationo fp yrroles from homopropargylic azidesb yana cetylenic Schmidt reaction. Scheme3.AuCl 3 -catalyzed preparation of fluorinated pyrroles.Scheme4.Pyrrole synthesis according to Aponick and Akai. REVIEWSHomogeneous Gold-Catalyzed Cyclization Reactions of Alkynes Scheme 32. Formationo fp yrroles via 5-exo-dig cyclization with acationic Au(I) catalyst.Scheme 33. Formationo fhomoallylic pyrroles via aza-Claisen rearrangement according to Gagosz. REVIEWSHomogeneous Gold-Catalyzed Cyclization Reactions of Alkynes Scheme 58. Au-catalyzed hydroamination in the total synthesis of (À)-Quinocarcin.Scheme 59. Reactionb etween o-alkynylbenzaldehydes and anilines under AuCl catalysis.Scheme60. Intramolecular hydroamination and transfer hydrogenation. REVIEWSHomogeneous Gold-Catalyzed Cyclization Reactions of Alkynes Scheme 79. Generation of ac ontact ion pair with retention of stereochemistry,a nd the unobserved sigmatropicr earrangement with inversion of stereochemistry.Scheme 80. Au(III)-catalyzed cycloisomerization with formation of dihydrothiazoles.Scheme81. Au(I)-catalyzed generation of an Au-carbene.

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Gold-Catalyzed Domino Aminocyclization/1,3-Sulfonyl Migration of N-Substituted N-Sulfonyl-aminobut-3-yn-2-ols to 1-Substituted 3-Sulfonyl-1H-pyrroles

Cited by 56 publications

References 57 publications

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

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

Skeletal reorganization divergence of N-sulfonyl ynamides

Homogeneous Gold‐Catalyzed Cyclization Reactions of Alkynes with N‐ and S‐Nucleophiles

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