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

Several types of nitrogen-, oxygen-, and sulfur-functionalized silyllithiums have been prepared as the first members of stable and/or well-characterizable functionalized silyl anions. These functionalized silyllithiums can be obtained mainly by tin-lithium exchange reaction of the corresponding silylstannanes with butyllithium and/or by reaction of the corresponding chlorosilanes with lithium. Described herein are also the general aspects of (1) high stability of [(amino) silyl]lithiums, (2) low stability of [(alkoxy)silyl]lithiums, behaving as silylenoid species, (3) low stability of [(arylthio)silyl]lithiums, affording silylenes, (4) structure analyses of the [(amino) silyl]lithiums in solution and in the solid state, (5) [2,3]-sila-Wittig rearrangement and cyclopropanation reaction of [(allyloxy)silyl]lithiums and the chirality transfer during these reactions, (6) functionalized oligosilane synthesis using [ (amino) silyl] lithiums, and (7) synthetic application of (aminosilyl) lithiums as a hydroxy anion equivalent by a combination with the oxidative cleavage of the Si-C bonds.