A synthetically convenient approach for the direct α-deuteration of amides is reported. This mechanistically unusual process relies on a retro-ene-type process, triggered by the addition of deuterated dimethyl sulfoxide to a keteniminium intermediate, generated through electrophilic amide activation. The transformation displays broad functional-group tolerance and high deuterium incorporation.
Keywords: amide activation; chemoselectivity; deuteration; sulfoxide isotopic labelling.
© 2020 The Authors. Published by Wiley-VCH GmbH.