137122-67-9Relevant academic research and scientific papers
Carboxylation with CO2 via brook rearrangement: Preparation of α-hydroxy acid derivatives
Mita, Tsuyoshi,Higuchi, Yuki,Sato, Yoshihiro
supporting information, p. 14 - 17 (2014/01/23)
In the presence of CsF, a wide range of α-substituted α-siloxy silanes were carboxylated under a CO2 atmosphere (1 atm) via Brook rearrangement. A variety of α-substituents including aryl, alkenyl, and alkyl groups were tolerated to afford α-hydroxy acids in moderate-to-high yields. One-pot synthesis from aldehydes using PhMe2SiLi and CO 2 was also possible, providing α-hydroxy acids without the isolation of an α-hydroxy silane.
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 (2007/10/02)
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.
