A two-step protocol for the conversion of alkyl-substituted alkynes to 1,3-enynes is reported. In this α-methenylation process, an iron-catalyzed propargylic C-H functionalization delivers tetramethylpiperidine-derived homopropargylic amines which undergo facile Cope elimination upon N-oxidation to afford the enyne products. A range of aryl alkyl and dialkyl acetylenes were found to be suitable substrates for this process, which constitutes an alkyne analogue for the Eschenmoser methenylation of carbonyl derivatives. In addition, a new bench-stable precatalyst for iron-catalyzed propargylic C-H functionalization is reported.
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| http://dx.doi.org/10.1021/acs.orglett.4c00696 | DOI Listing |
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