Under neat conditions: The aerobic and room temperature compatible double addition of s-block organometallic reagents into nitriles, in the absence of any external organic solvent, is reported. Thus, direct conversion of nitriles into asymmetric tertiary alcohols is achieved through a one-pot/two-steps modular process, without tedious and energy consuming halfway isolation/purification steps needed.
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.Zum Volltext