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A Stereospecific Alkene 1,2‐Aminofunctionalization Platform for the Assembly of Complex Nitrogen‐Containing Ring Systems

Yuxiang Zhu, Matthew J. S. Smith, Wenbin Tu, John F. Bower

2023Angewandte Chemie International Edition22 citationsDOIOpen Access PDF

Abstract

Abstract TFA promoted deprotection of O−Ts activated N‐Boc hydroxylamines triggers aminofunctionalization‐based polycyclizations of tethered alkenes. The processes involve intramolecular stereospecific aza‐Prilezhaev alkene aziridination in advance of stereospecific C−N cleavage by a pendant nucleophile. Using this approach, a wide range of fully intramolecular alkene anti ‐1,2‐difunctionalizations can be achieved, including diaminations, amino‐oxygenations and amino‐arylations. Trends associated with the regioselectivity of the C−N cleavage step are outlined. The method provides a broad and predictable platform for accessing diverse C(sp 3 )‐rich polyheterocycles of relevance to medicinal chemistry.

Topics & Concepts

AlkeneStereospecificityIntramolecular forceRegioselectivityChemistryCleavage (geology)StereochemistryNucleophileRing (chemistry)Organic chemistryBiologyCatalysisPaleontologyFracture (geology)Synthesis and Catalytic ReactionsCatalytic C–H Functionalization MethodsAlkaloids: synthesis and pharmacology
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