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Synthesis 2024; 56(01): 134-142
DOI: 10.1055/a-2022-1905
special topic
Advances in Skeletal Editing and Rearrangement Reactions

Palladium-Catalyzed Unimolecular Fragment Coupling of N-Allylamides Bearing a Tethered Nucleophile with the Translocation of an Amide Group

Ryoma Shimazumi
a   Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871, Japan
,
Takuya Kodama
a   Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871, Japan
b   Innovative Catalysis Science Division, Institute for Open and Transdisciplinary Research Initiatives (ICS-OTRI), Osaka University, Suita, Osaka 565-0871, Japan
,
Mamoru Tobisu  ∗
a   Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871, Japan
b   Innovative Catalysis Science Division, Institute for Open and Transdisciplinary Research Initiatives (ICS-OTRI), Osaka University, Suita, Osaka 565-0871, Japan
› Author AffiliationsThis work was supported by the Japan Society for the Promotion of Science (JSPS KAKENHI; grant number JP21H04682) from MEXT, Japan­. R.S. thanks the Japan Science and Technology Agency (JST SPRING; grant number JPMJSP2138) for support.
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Abstract

The palladium-catalyzed reaction of N-allylamides bearing a tethered nucleophile results in the extrusion of an amide moiety in the form of an isocyanate, with its subsequent capture by the pendant nucleophile­. This reaction involves the net catalytic transposition of an amide group.

Key words

palladium catalyst - C–N bond activation - amides - isocyanates - elimination - rearrangement

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/a-2022-1905.
  • Supporting Information


Publication History

Received: 19 November 2022

Accepted after revision: 30 January 2023

Accepted Manuscript online:
30 January 2023

Article published online:
06 March 2023

© 2023. Thieme. All rights reserved

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