0000000001073046
AUTHOR
Yiyin Xia
Enantiospecific Brook Rearrangement of Tertiary Benzylic α-Hydroxysilanes
The Brook rearrangement of simple, chiral tertiary benzylic -hydroxysilanes is presented. The rearrangement followed by proton trapping is enantiospecific and proceeds with inversion of the configuration at the carbon center. Importantly, the [1,2]-Brook rearrangement can be followed by trapping of methyl or allyl electrophiles even in the protic environment, although with minimal retention of chirality.
Taming conformational heterogeneity in and with vibrational circular dichroism spectroscopy
Chemical science 10, 7680 -7689 (2019). doi:10.1039/C9SC02866H
Regional Susceptibility in VCD Spectra to Dynamic Molecular Motions
Experimental and theoretical studies of the vibrational circular dichroism (VCD) spectrum of 3-methyl-1-(methyldiphenlsilyl)-1-phenylbutan-1-ol, whose absolute configuration is key to elucidating the Brook rearrangement of tertiary benzylic α-hydroxylsilanes, are presented. It is found that the entire OH-bending region in this spectrum—a region that provides important marker bands—cannot be reproduced at all by standard theoretical approaches even though other regions are well described. Using a novel approach to disentangle contributions to the rotational strength of these bands, internal coordinates are identified that critically influence the appearance of this part of the spectrum. We s…