Tertiary Alkylations of Aldehydes, Ketones or Imines Using Benzylic Organoboronates and a Base Catalyst

The KHMDS-catalyzed tertiary alkylation of aldehydes, ketones or imines using tertiary benzylic organoboronates is reported. This protocol permitted the use of tertiary benzylic alkylboronates as the tertiary alkyl anion for construction of highly congested contiguous sp(3) carbon centers. The mild and transition-metal-free reaction conditions are attractive features of the protocol.