Stereoselective Synthesis of Less Accessible α-Tertiary Amino Ketimines via Electrophilic Amination of α-Branched N-tert-Butanesulfinyl Ketimines

A stereocontrolled electrophilicamination of alpha-branched N-tert-butanesulfinyl ketimines was developedto construct alpha-aminoketone derivatives containing less accessible alpha-tetrasubstituted stereocenters. Stereospecific alpha-deprotonationof ketimines with potassium tert-butoxide gave stereodefinedmetalloenamine intermediates that could act as nucleophiles to attackazodicarboxylic derivatives, affording alpha-aminated products inhigh yields with excellent stereoselectivities.

Automated summary

A stereocontrolled electrophilic amination approach was employed for the synthesis of α-aminoketone derivatives with less accessible α-tetrasubstituted stereocenters. Stereospecific α-deprotonation of ketimines followed by nucleophilic attack of azodicarboxylic derivatives afforded α-aminated products in high yields with excellent stereoselectivities.