A DFT study on the formation of heterocycles via iodine( iii )-promoted ring expansion reactions

The ring expansion of bicyclic heterocycles bearing an exocyclic double bond promoted by Koser's reagent [hydroxy(tosyloxy)iodobenzene, HTIB] is a mild, practical, and metal-free methodology to access seven-membered rings containing fused furan, indole, pyrrole, and thiophene heterocycles provi...

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Bibliographic Details
Published in:New journal of chemistry 2022-11, Vol.46 (43), p.20817-20827
Main Authors: Lussari, Natália, Khan, Ajmir, Pilli, Ronaldo A., Dos Santos, Alcindo A., Silva, Luiz F., Braga, Ataualpa A. C.
Format: Article
Language:English
Subjects:
Acetonitrile
Iodine
Methanol
Natural products
Reagents
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Summary:The ring expansion of bicyclic heterocycles bearing an exocyclic double bond promoted by Koser's reagent [hydroxy(tosyloxy)iodobenzene, HTIB] is a mild, practical, and metal-free methodology to access seven-membered rings containing fused furan, indole, pyrrole, and thiophene heterocycles providing an entry to structurally challenging bioactive natural products as well as pharmaceuticals. Here we describe our DFT results for the reaction conducted in aqueous methanol (95 : 5 v/v). These computational studies involving the microsolvation approach validated the regiochemistry of such kinetically favored rearrangements and helped to explain the faster reaction rate observed in aqueous methanol when compared to aqueous acetonitrile showcasing a fundamental role of protic solvents during the nucleophilic addition step which may support further experimental studies.
ISSN:1144-0546
1369-9261
DOI:10.1039/D2NJ04393A