Room Temperature Intramolecular Hydro-O-alkylation of Aldehydes:  sp³ C−H Functionalization via a Lewis Acid Catalyzed Tandem 1,5-Hydride Transfer/Cyclization

The scope and limitations of intramolecular hydro-O-alkylation of aldehyde substrates leading to spiroketals and bicyclic ketals and aminals is reported. The direct transformation of tertiary and sterically hindered secondary sp³ C−H bonds into C−O bonds under the action of a catalytic amount of a variety of Lewis acids is described. The mechanism of these transformations is proposed to involve a tandem hydride transfer/cyclization sequence.