Stereocontrolled Construction of Acyclic Quaternary Carbon Centers via α-Hydroxymethylation of α-Branched N-tert-Butanesulfinyl Ketimines.

Hydroxymethylation of α-branched N-tert-butanesulfinyl ketimines with formaldehyde equivalents was developed to stereoselectively construct acyclic quaternary stereocenters bearing two sterically and electronically similar substituents. The stereoselective tBuOK-promoted α-deprotonation of acyclic ketimines allowed for the stereodefined formation of fully substituted aza-enolates, followed by facially selective C-C bond formation involving formaldehyde formed in situ, yielding α-hydroxymethylated products with precise stereocontrol.