A mild one-pot transformation of nitroalkanes to ketones or aldehydes via a visible-light photocatalysis–hydrolysis sequence

Abstract

Using a visible-light photoredox catalysis strategy with household decorative blue LEDs and the additives Et₃N and DIPEA, as well as the subsequent hydrolysis sequence, a mild one-pot process for the direct transformation of nitroalkanes to the corresponding ketones and aldehydes, constituting a Nef-like reaction, has been developed. It is worth noting that by using an appropriate photocatalyst (e.g., [Ir(dtbbpy)(ppy)₂]PF₆) and the extra additive Et₃N with the combination of DIPEA and Mg(ClO₄)₂ in i-PrOH (instead of CH₃CN), the transformation of nitroalkanes to the corresponding oximes, rather than nitrones, can be markedly more effective. The oximes can then be hydrolyzed to ketones by reaction with CuCl₂·2H₂O in a pH 7 buffer solution. This process is appealing because of the benefits of efficient conversion, mild conditions, high yields, and general applicability to compounds with a wide range of labile functional groups.