Cleavage of the silicon-carbon bond by fluoride ion in triorganosilyloxiranes. The stereochemistry of substitution at oxiranyl carbon.

Ring opening reactions of 2-trialkylsilylaziridines

“…Such behaviour is well documented for the corresponding 2-trialkylsilylepoxides. 21 However, we found that fluorodesilylation of other 2-trialkylsilylaziridines was not an easy reaction to perform and this was the only simple aziridine, 11, (R 1 = H or Ph, R 2 = Ph, Pr or CO 2 Et) to undergo such a reaction. Alkali metal fluorides and tetrabutylammonium fluoride were employed under a range of conditions, including rigorous drying, 22-25 however no reaction was observed.…”

Stereochemical Control in Organic Synthesis Using Silicon-Containing Compounds

“…When anion-stabilizing groups are present, the silyl group can be easily displaced, but the stereochemistry is usually lost, as with α-silyl ketones and esters, which give trigonal enols or enolate ions. The same loss of configuration appears also to take place when a silyl group is removed from α-silyl sulfones, but the sulfide groups in the alcohols 750 and 751 allow the configuration to be retained (Scheme ), and protodesilylation usefully takes place with retention of configuration from α-silyl epoxides, as in the reaction 274 → 272 in Scheme , and this reaction has been much used in synthesis, with or without the Sharpless asymmetric epoxidation 186 …”

Copper‐Catalyzed Enantioselective Hydrosilylation of gem‐Difluorocyclopropenes Leading to a Stereochemical Study of the Silylated gem‐Difluorocyclopropanes

“…Scheme 4 displays the desilylation of 2 a, 2 b, and 2 l by TBAF. As one of the comparable reports suggested, [26] desilylation with fluoride ion proceeds via retention of configuration. However, all the examined substrates provided the corresponding gem-difluorocyclopropane 4 a, 4 b, and 4 l in moderate yields but accompanied decrease of enantiomeric purity.…”