Ynamides are nitrogen atom substituted alkynes in which the nitrogen atom is neighboring an amide or sulfonamide. Ynamides are known to be incredibly reactive yet stable, are fairly easy to synthesize, and can form complex ring systems via cycloaddition reactions. Additionally, ynamides allow for modification of a molecule with simultaneous introduction of another functional group. A structural variation of ynamides that would allow for the introduction of even more functionality are halogenated ynamides. These halo-ynamides, however, have rarely been synthesized despite their potential use for production of biologically relevant molecules such as pharmaceuticals. Halo-ynamides, thus far, have been made via a two-step reaction sequence with the addition or in-situ generation of the alkyne followed by the attachment of a halogen to the terminal position.<br/>In this project, the goal was to synthesize halogenated ynamides in a one-step haloalkynylation utilizing existing methodology that uses hypervalent iodonium salts such as ethynyl(phenyl)iodonium triflate but including a halide on the alkyne moiety. After initial reaction optimizations, our newly developed protocol has proven highly successful, yielding up to 70% product of aniline derived haloalkynes. During development of the original haloalkynylation protocol in our lab issues were encountered upon the haloalkynylation of aliphatic as well as benzylic amines. The overall goal of this project is to develop a protocol that allows for the synthesis of all halo-ynamides besides fluorides as the ability of introducing three different halides will allow for fine tuning of the stability of the resulting products and enable an increased scope of our haloalkynylation protocol. All initial efforts in reaction development have centered around the synthesis of brominated ynamides using bromoethynyl(phenyl)iodonium triflate. However, preliminary results with iodoethynyl(phenyl)iodonium triflate suggest that the same haloalkynylation is possible irrespective of the appended halide and we expect to be able to showcase our results for the synthesis of chloro-, bromo-, and iodoynamides in the spring of 2020.

New method of synthesizing haloynamides via brominated, iodinated, and chlorinated triflate salts

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

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