106484-73-5Relevant articles and documents
1,3-γ-Silyl-elimination in electron-deficient cationic systems
Mercadante, Michael A.,Kelly, Christopher B.,Hamlin, Trevor A.,Delle Chiaie, Kayla R.,Drago, Michael D.,Duffy, Katherine K.,Dumas, Megan T.,Fager, Diana C.,Glod, Bryanna L. C.,Hansen, Katherine E.,Hill, Cameron R.,Leising, Rebecca M.,Lynes, Catherine L.,Macinnis, Allyson E.,McGohey, Madeline R.,Murray, Stephanie A.,Piquette, Marc C.,Roy, Shaina L.,Smith, Ryan M.,Sullivan, Katherine R.,Truong, Bao H.,Vailonis, Kristina M.,Gorbatyuk, Vitaliy,Leadbeater, Nicholas E.,Tilley, Leon J.
, p. 3983 - 3994 (2014)
Placement of an electron-withdrawing trifluoromethyl group (-CF 3) at a putative cationic centre enhances γ-silyl neighbouring-group participation (NGP). In stark contrast to previously studied γ-silyl-substituted systems, the preferred reaction pathway is 1,3-γ-silyl elimination, giving ring closure over solvent substitution or alkene formation. The scope of this cyclopropanation reaction is explored for numerous cyclic and acyclic examples, proving this method to be a viable approach to preparing CF3-substituted cyclopropanes and bicyclic systems, both containing quaternary centres. Rate-constants, kinetic isotope effects, and quantum mechanical calculations provided evidence for this enhancement and further elaborated the disparity in the reaction outcome between these systems and previously studied γ-silyl systems.
Stereoselective synthesis of (Z)- and (E)-allylic silanes by copper- mediated substitution reactions of allylic carbamates with grignard reagents
Smitrovich, Jacqueline H.,Woerpel
, p. 1601 - 1614 (2007/10/03)
Both (Z)- and (E)-allylic silanes were prepared with high stereoselectivity by the copper-mediated substitution of allylic carbamates by organometallic reagents. The reaction of alkylmagnesium reagents with (E)- allylic carbamates provides (Z)-allylic silanes, whereas both alkylmagnesium and alkyllithium reagents react with (Z)-allylic carbamates to afford (E)- allylic silanes. Because Grignard reagents are often more facile to prepare than alkyllithium species, these reagents are the optimal nucleophiles for the synthesis of both (Z)- and (E)-allylic silanes. This method also allows readily available nonracemic allylic carbamates to be converted to chiral, nonracemic (Z)- and (E)-allylic silanes with high stereoselectivity.
Diastereoselective Aldol Reactions of β-Silylenolates: A Formal Synthesis of Thienamicin
Fleming, Ian,Kilburn, Jeremy D.
, p. 1198 - 1199 (2007/10/02)
The lithium enolate (1) of benzyl β-phenyldimethylsilylbutanoate reacts with β-phenyldimethylsilylpropionaldehyde (2) to give, with high diastereoselectivity, the aldol product (3), which is converted into the β-lactam (7), a known precursor of thienamyci
