Regiospecific photosensitized oxygenation of vinylsilanes. A method for converting saturated ketones to 1,2-transposed allylic alcohols. Possible role of silicon in directing the regioselectivity of epoxysilane cleavage reactions

Synthesis of a 35-Member Stereoisomer Library of Bistramide A: Evaluation of Effects on actin State, Cell Cycle and Tumor Cell Growth

“…43 Alternatively, formation of a pentacoordinated silicon followed by 1,2-migration was also postulated. 45 Lastly, X-ray crystal structure 46 and gas phase and theoretical studies 47 showed the α C-O bond (adjacent to the Si) to be longer and weaker than the β C-O bond. Our particular system has the added advantage of a Lewis basic site on the adjacent carbonyl to aid in opening via coordination of resident metal centers.…”

One‐Pot Synthesis of 2,7‐Dioxabicyclo[2.2.1]heptanes from Oxoallylsilanes

“…[23] This fact is in sharp contrast to the expected β cleavage due to the known stabilization of carbocations β to silicon. [24] Paquette and co-workers [25] reported that the C-Si and the neighbouring C-O bonds in α,β-silyl epoxides are not favourably aligned for stabilization of the developing cation β to silicon. Moreover, in our case, α-opening of the silyl epoxide 8 by the carbonyl group is not favourable for steric reasons, because the bulky silyl group partially blocks the rear face of the epoxide, making difficult the approach of the carbonyl group.…”

Biomimetic Synthesis of Polyether Natural Products via Polyepoxide Opening

“…Capitalizing on the effects of a silyl group attached directly to an epoxide, studied in detail by Hudrlik [188,189] and Paquette [190], Jamison developed an iterative approach to the synthesis of trans-fused oligo(tetrahydropyran) fragments (Scheme 15.14c) [18]. In contrast to cyclization of epoxysulfones, in which the sulfone deactivates the undesired site of epoxide opening, silyl groups stabilize positive charge in the transition state leading to 6-endo epoxide opening.…”