Selective ketyl couplings pose an issue due to the strongly reducing conditions necessary for single electron reduction of carbonyls. In order to lower the reduction potential of aldehydes (Ered &gt; –2.0 V), we developed an activation strategy to generate α-oxy iodides as a ketyl radical precursor (Ered &gt; –1.1 V). Utilizing a milder protocol, ketyl radical couplings with alkynes was achieved in a redox-neutral fashion to provide access to atom transfer radical addition (ATRA) products, vinyl iodides. Employing a photoredox catalyst, these synthetically valuable cross coupling handles were achieved favoring the Z-selective adduct from feedstock aldehydes and diverse alkyne coupling partners.

Redox-neutral aldehyde couplings

255th National Meeting (2018)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.