Synthesis of β-mannopyranosides from α-epimers by radical inversion

Methodology Development and Physical Organic Chemistry: A Powerful Combination for the Advancement of Glycochemistry

“…Curran and coworkers contemporaneously adopted a parallel approach to the inversion of α- to β-mannosides based on 1,6-hydrogen atom abstraction with a benzyl radical precursor located on O2 and encountered the analogous problem, namely competing 1,5-hydrogen abstraction from the 2-position. 29 …”

Functionalization of the Anomeric C–H Bond of Carbohydrates: Old Strategies and New Opportunities

“…15 Later, Curran 16 and Crich 17 and their coworkers independently reported the anomerization of α-mannosides following a C-H bond activation pathway. Their approach was based on the temporary anchoring of a radical at position 2 to promote the 1,5-abstraction of the equatorial anomeric hydrogen atom.…”

(1-Bromoethenyl)chlorodimethylsilane

“…Reaction with Alcohols. 5 Theoretical calculations by Shuto revealed that the vinylic C(1)-H bond dissociation energy is significantly lowered by the substitution of the silyl moiety. 1 The resulting silyl ethers serve as useful intermediates in organic synthesis.…”