Oxidative Rearrangement Approach for the Ring Contraction of N−H Piperidines to Pyrrolidines

We have developed a method for ring contraction of N−H piperidines using oxidative rearrangement with PhI(OAc)2. The reaction forms iminium ion intermediates that are effectively trapped by nucleophiles (e. g., NaBH4, H2O) yielding the corresponding pyrrolidine derivatives. Additionally, we propose...

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Bibliographic Details
Published in:Advanced synthesis & catalysis 2024-08, Vol.366 (15), p.3325-3331
Main Authors: Takashima, Mirei, Miyoshi, Makoto, Sako, Makoto, Arisawa, Mitsuhiro, Murai, Kenichi
Format: Article
Language:English
Subjects:
Amines
Density functional theory
Heterocycles
Hypervalent iodine reagent
Nucleophiles
Rearrangement
Ring contraction
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Summary:We have developed a method for ring contraction of N−H piperidines using oxidative rearrangement with PhI(OAc)2. The reaction forms iminium ion intermediates that are effectively trapped by nucleophiles (e. g., NaBH4, H2O) yielding the corresponding pyrrolidine derivatives. Additionally, we propose an ionic mechanism supported by experiments and density‐functional theory calculations.
ISSN:1615-4150
1615-4169
DOI:10.1002/adsc.202400484