ChemInform Abstract: REGIOSELECTIVE HYDROSILYLATION‐DESILYLATION: CONVENIENT PREPARATION OF A 2‐(TRIMETHYLSILYL)‐1‐ALKENE

Abstract

Die Hydrosilylierung des Alkins (I) liefert das Bissilylderivat (II), aus dem mit Säure oder auch mit deuterierten Verbindungen die Spaltprodukte (III) entstehen, die z.B. in Form des Epoxides (IV) strukturell sichergestellt werden.

Metalated Heterocycles and Their Applications in Synthetic Organic Chemistry

“…Thus, (trimethylsilyl)diazomethane ( 291 ) adds directly to N -sulfonylimines, such as 290 , to afford the corresponding silylaziridine 292 with 95:5 cis -stereoselectivity. , When these kinds of silylaziridines react with a flouride source such as triphenyltrifluorosilicate (TBAT), an azirinidyl anion is formed, being able to react with electrophiles such as benzaldehyde, affording the corresponding alcohol 293 with retention of the preliminary cis -configuration and also with high diastereoselectivity at the newly created stereocenter (Scheme ) . In addition, epoxysilanes, , can be transformed into oxiranyl anions by treatment with fluoride as mentioned previously, examples being the generation of an oxiranyl anion from a (trimethylsilyl)epoxylactone and tetra- n -butylammonium fluoride (TBAF) and its reaction with aldehydes, or the recent TBAF-mediated generation of an amide carbonyl-stabilized oxiranyl anion 79 …”