137122-47-5Relevant articles and documents
Thermal Rearrangements of α-(Acyloxy)silanes. 2. Formation of Chiral Precursors and Migratory Preference of Silicon-Based Groups
Buynak, John D.,Strickland, J. Byron,Lamb, Grady W.,Khasnis, Dipti,Modi, Seema,et al.
, p. 7076 - 7083 (1991)
The asymmetric reduction of acylsilanes to chiral α-hydroxysilanes and the thermal rearrangement of the corresponding chiral α-acetoxysilanes was employed.Ipc2BCl reduces many acylsilanes in > 95percent ee.The rate of the thermal rearrangement of the α-acetoxysilanes was dependent upon the substituents at both silicon and carbon.Evidence is presented to indicate there is electron deficiency at the α-carbon in the transition state.Migratory aptitudes follow those expected on the basis of the migrating group assuming an apical migratory group at a pentacoordinate silicon.A previously unreported hydrolytic transformation of a proposed acylsilyl hydride to a stable 1-sila-1,2-diol was observed.
