Summary: Metalation of diorganostannanes R1# nH2 by lithium diisopropylamide afforded the corresponding (diorganostannyl) lithiums, R1# nHLi. Further reaction with halides led to unsymmetrically substituted alkyldiorganostannanes, Rla2SnH. In situ stepwise dimetalation of diorganostannanes R1# nH2gave the expected diallzylation products R1a2# n with organic halides, aldehydes, and epoxides.