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Gold-Catalyzed [3,3]-Sigmatropic Rearrangement of <i>ortho</i>-Alkynyl-<i>S</i>,<i>S</i>-diarylsulfilimines

Alexandra V. Mackenroth, Patrick W. Antoni, Frank Röminger, Matthias Rudolph, A. Stephen K. Hashmi

2023Organic Letters16 citationsDOI

Abstract

Highly functionalized 5 H -pyrrolo[2,3- b ]pyrazine cores, carrying a diaryl sulfide moiety at the C-7 position, were obtained from a gold-catalyzed reaction using easily accessible ortho -alkynyl-substituted S, S -diarylsulfilimines as intramolecular nitrene transfer reagents for the first time. The reaction proceeds under mild conditions, providing excellent yields while tolerating a large variety of different substitution patterns. We provide experimental evidence for an intramolecular reaction mechanism, likely including an unprecedented gold-catalyzed amino sulfonium [3,3]-sigmatropic rearrangement.

Topics & Concepts

SulfoniumChemistryIntramolecular forceSigmatropic reactionPyrazineNitreneMoietyCatalysisCombinatorial chemistryMedicinal chemistryStereochemistryOrganic chemistrySalt (chemistry)Synthesis and Catalytic ReactionsSulfur-Based Synthesis TechniquesCatalytic Alkyne Reactions