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Synfacts 2022; 18(09): 0975
DOI: 10.1055/s-0042-1755652
Metals in Synthesis

Extrusion of Isocyanate from N-Allyl Amides Enables π-Allyl Palladium Chemistry!

Contributor(s):
Martin Oestreich
,
Hendrik F. T. Klare
,
Phillip Pommerening
Shimazumi R, Tanimoto R, Kodama T, Tobisu M. * Osaka University, Japan
Palladium-Catalyzed Unimolecular Fragment Coupling of N-Allylamides via Elimination of Isocyanate.

J. Am. Chem. Soc. 2022;
144: 11033-11043
DOI: 10.1021/jacs.2c04527.
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Key words

amides - isocyanate elimination - palladium catalysis - unimolecular fragment coupling

Significance

A palladium(0)-catalyzed unimolecular fragment coupling (UFC) reaction of N-allyl amides through the elimination of an isocyanate ­is reported. Recombination of the resulting fragments leads to C–N, C–C, and C–S bond formation in good to high yields. The synthetic value of this protocol is highlighted by the late-stage conversion of amides into allyl groups.


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Comment

Besides Pd(PPh3)4, Ni(cod)2 can also be used as the catalyst. Several control experiments under palladium catalysis were performed, supporting the shown mechanism. The use of nickel as transition metal eventually allowed the crystallographic characterization of the cationic π-allyl intermediate.


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Publication History

Article published online:
18 August 2022

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