Photocatalytic Synthesis of Acetals and Ketals from Aldehydes and Silylenolethers without the Use of Acids

Use light instead of acids: Silylenolethers derived from aldehydes and ketones as well as aldehydes themselves react efficiently to give acetals in good to excellent yields. The substrate range with respect to both aldehydes and alcohols is broad, and acid- and hydrogen-labile protecting groups are tolerated.

Abstract

Acetals and ketals are among the most important protecting groups for carbonyl compounds. A new method for acetalization and ketalization by means of photoredox catalysis has been developed. A biscyanolated perylene bisimide is used as an electron-poor photocatalyst, together with green light (525 nm LED). Silylenolethers derived from aldehydes react efficiently to give acetals in good to excellent yields. A broad substrate range was shown with respect to both the aldehydes and the alcohols. The functional group tolerance is high; in particular, acid- and hydrogen-labile protecting groups are tolerated. Aldehydes can also be directly and selectively converted into the respective acetals. Only ketones must be converted to their silylenolethers before ketalization. This photocatalytic method works without any use of acids or photoacids, and does not need any additives or H-atom transfer reagents. Hence, it broadens the substrate scope and repertoire of photoredox catalysis with respect to carbonyl chemistry.

Zum Volltext