Copper(I)‐Catalyzed Allylic Substitution of Silyl Nucleophiles through SiSi Bond Activation

Abstract

We report the first copper(I)-catalyzed reaction between a disilane and allylic carbonates to produce allylsilanes. The silyl nucleophilic substitution proceeded primarily in a S N 2 fashion whereas S N 2' products were also obtained through s-p-s isomerization of the copperA C H T U N G T R E N N U N G (III) intermediate depending on the substrates steric bulk.

Strain-Activated Diels–Alder Trapping of 1,2-Cyclohexadienes: Intramolecular Capture by Pendent Furans

“…Finally, a substrate lacking any oxygen substitution on the allene precursor was prepared. In this short route, cyclohexanone 6a was subjected to Luche reduction and conversion of the alcohol to the corresponding carbonate, followed by direct displacement of the allylic carbonate with silylcuprate, to afford 1j .…”

Recent Progress in the Transition‐Metal‐Catalyzed Activation of Si−Si Bonds To Form C−Si Bonds

“…Ito and co-workersd isclose am ethod fort he copper(I)-catalyzed nucleophilic silylation of allylic carbonates with dimethylphenyldisilane (Scheme 24). [37] The combination of CuCl (5 mol %) as the catalysta nd KOtBu (1.0 equiv.) as an additive is essential for obtainingo ptimal yields of the desired allylsi-lanes.…”

“…Ito and co‐workers disclose a method for the copper(I)‐catalyzed nucleophilic silylation of allylic carbonates with dimethylphenyldisilane (Scheme ) . The combination of CuCl (5 mol %) as the catalyst and KO t Bu (1.0 equiv.)…”

A Mild Method for the Generation and Interception of 1,2-Cycloheptadienes with 1,3-Dipoles

“…Treatment of this intermediate with silyl cuprate reagent resulted in efficient conversion to 10 . This transformation proceeds via either direct S N 2 displacement of carbonate or an S N 2′ reaction with allylic transposition to afford 10 . , …”