Aerobic/Room‐Temperature‐Compatible s‐Block Organometallic Chemistry in Neat Conditions: A Missing Synthetic Tool for the Selective Conversion of Nitriles into Asymmetric Alcohols

Highly‐efficient and selective one‐pot/two‐step modular double addition of different highly polar organometallic reagents (RLi/RMgX) to nitriles en route to asymmetric tertiary alcohols (without the need for isolation/purification of any halfway reaction intermediate) has been studied, for the first time, in the absence of external/additional organic solvents (neat conditions), at room temperature and under air/moisture (no protecting atmosphere is required), which are generally forbidden reaction conditions in the field of highly‐reactive organolithium/organomagnesium reagents. The one‐pot modular tandem protocol demonstrated high chemoselectivity with a broad range of nitriles, as no side reactions (Li/halogen exchange, ortho‐lithiations or benzylic metalations) were detected. Finally, this protocol could be scaled up, thus proving that this environmentally friendly methodology is amenable for a possible applied synthesis of asymmetric tertiary alcohols under bench type reaction conditions and in the absence of external organic solvents.