Synthesis, structures, and reactions of nitrogen, oxygen, and sulfur-functionalized silyl anions

Several types of nitrogen-, oxygen-, and sulfur-functionalized silyllithium s have been prepared as the first members of stable and/or well-characteriz able functionalized silyl anions. These functionalized silyllithiums can be obtained mainly by tin-lithium exchange reaction of the corresponding sily lstannanes with butyllithium and/or by reaction of the corresponding chloro silanes with lithium. Described herein are also the general aspects of (1) high stability of [(amino) silyl]lithiums, (2) low stability of [(alkoxy)si lyl]lithiums, behaving as silylenoid species, (3) low stability of [(arylth io)silyl]lithiums, affording silylenes, (4) structure analyses of the [(ami no) silyl]lithiums in solution and in the solid state, (5) [2,3]-sila-Witti g rearrangement and cyclopropanation reaction of [(allyloxy)silyl]lithiums and the chirality transfer during these reactions, (6) functionalized oligo silane synthesis using [ (amino) silyl] lithiums, and (7) synthetic applica tion of (aminosilyl) lithiums as a hydroxy anion equivalent by a combinatio n with the oxidative cleavage of the Si-C bonds.