scholarly journals A Photochemical Ring Expansion of 6- to 8-Membered Nitrogen Heterocycles by [1,3]-Sigmatropic Rearrangement.

2021 ◽  
Author(s):  
David Harrowven ◽  
Wei Sun ◽  
Mark E. Light ◽  
Morgan Manning
Keyword(s):  
Nitrogen Heterocycles ◽  
Ring Expansion ◽  
Sigmatropic Rearrangement

A new route to azocines and benzoazocines from furopyridinones is described through a photochemically induced [1,3]-sigmatropic rearrangement. The method gives access to these 8-membered nitrogen heterocycles from dimethyl squarate in...

scholarly journals Intermolecular 3+3 Ring Expansion of Aziridines to Dehydropiperidines through the Intermediacy of Aziridinium Ylides

2019 ◽  
Author(s):  
Jennifer Schomaker ◽  
Josephine Eshon ◽  
Kate A. Nicastri ◽  
Steven C. Schmid ◽  
William T. Raskopf ◽  
...  
Keyword(s):  
Natural Product ◽  
Functional Group ◽  
Ring Expansion ◽  
Sigmatropic Rearrangement ◽  
Reactive Intermediate ◽  
Mechanistic Studies ◽  
Reaction Conditions ◽  
Complex Molecules ◽  
Form Complex ◽  
Reaction Proceeds

Bicyclic aziridines undergo formal [3+3] ring expansion reactions when exposed to rhodium-bound vinyl carbenes to form complex dehydropiperidines in a highly stereocontrolled rearrangement. Mechanistic studies and DFT computations indicate the reaction proceeds through the formation of a vinyl aziridinium ylide; this reactive intermediate undergoes a concerted, asynchronous, pseudo-[1,4]- sigmatropic rearrangement to directly furnish the heterocyclic products with net retention at the new C-C bond. In combination with an asymmetric silver-catalyzed aziridination developed in our group, this method quickly delivers enantioenriched scaffolds with up to three contiguous stereocenters. The mild reaction conditions, functional group tolerance, and high stereochemical retention of this method are especially well-suited for appending piperidine motifs to natural product and complex molecules. Ultimately, our work establishes the value of underutilized aziridinium ylides as key intermediates in strategies to convert small, strained rings to larger N-heterocycles.

ChemInform Abstract: Medium-Ring Nitrogen Heterocycles Through Migratory Ring Expansion of Metalated Ureas.

ChemInform ◽  
2016 ◽  
Vol 47 (51) ◽  
Author(s):  
Jessica E. Hall ◽  
Johnathan V. Matlock ◽  
John W. Ward ◽  
Katharine V. Gray ◽  
Jonathan Clayden
Keyword(s):  
Nitrogen Heterocycles ◽  
Ring Expansion ◽  
Ring Nitrogen ◽  
Medium Ring
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