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. 2017 Apr 12;139(14):5133-5139.
doi: 10.1021/jacs.7b00564. Epub 2017 Apr 4.

Isomerization of N-Allyl Amides To Form Geometrically Defined Di-, Tri-, and Tetrasubstituted Enamides

Barry M Trost  1 , James J Cregg  1 , Nicolas Quach  1
Affiliations

Isomerization of N-Allyl Amides To Form Geometrically Defined Di-, Tri-, and Tetrasubstituted Enamides

Barry M Trost et al. J Am Chem Soc. .

Abstract

Enamides represent bioactive pharmacophores in various natural products, and have become increasingly common reagents for asymmetric incorporation of nitrogen functionality. Yet the synthesis of the requisite geometrically defined enamides remains problematic, especially for highly substituted and Z-enamides. Herein we wish to report a general atom economic method for the isomerization of a broad range of N-allyl amides to form Z-di-, tri-, and tetrasubstituted enamides with exceptional geometric selectivity. This report represents the first examples of a catalytic isomerization of N-allyl amides to form nonpropenyl disubstituted, tri- and tetrasubstituted enamides with excellent geometric control. Applications of these geometrically defined enamides toward the synthesis of cis vicinal amino alcohols and tetrasubstituted α-borylamido complexes are discussed.

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Conflict of interest statement

Notes

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Bioactive Enamide Natural Products
Figure 2
Figure 2
Isomerization of N-Allyl Amides
Figure 3
Figure 3
Formamide Directing Groups
Figure 4
Figure 4
Vinyl Boronates Substrate Synthesis
Figure 5
Figure 5
Isomerization of Vinyl Boronates
Figure 6
Figure 6
One-Pot Allylation
Figure 7
Figure 7
Hydroboration of tetrasubstituted enamide to form α-borylamido complex
Figure 8
Figure 8
Mechanistic Proposal
Figure 9
Figure 9
Additional Mechanistic Consideration
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