130496-62-7Relevant academic research and scientific papers
The triisopropylsilyl effect: Exceptional Cram-type selectivity in Mukaiyama aldol reactions of a silyl ketene thioacetal
Davis, Anthony P.,Plunkett, Stephen J.,Muir, Jayne E.
, p. 1797 - 1798 (1998)
The level of 1,2-asymmetric induction in the BF3·OEt2-promoted addition of silyl ketene thioacetals to α-asymmetric aldehydes is affected by the bulk of the silyl group; unprecedented Cram-type selectivity is given by the triisopropylsilyl derivative 8a.
On the Mechanism of Lewis Acid Mediated Nucleophilic Substitution Reactions of Acetals
Mori, Ichiro,Ishihara, Kazuaki,Flippin, Lee A.,Nozaki, Kyoko,Yamamoto, Hisashi,et al.
, p. 6107 - 6115 (2007/10/02)
Lewis acid mediated nucleophilic substitution of acetals can occur by direct displacement (SN2) or oxocarbenium ion (SN1) mechanisms.With acyclic acetals, stereoselectivity increases with increasing steric bulk of the alkoxy group and with increasing polarity of the reaction medium.The enhanced stereoselectivity observed with acetals of secondary and tertiary alcohols is explained by perturbation of the approach trajectory of the nucleophilic alkene as it attacks the oxocarbenium ion.Highest stereoselectivity is seen in the reaction of 2-(1-phenylethyl)-4,4,5,5-tetramethyl-1,3-dioxolane (4) with enol silane 5; only one diastereomeric product (9s) is obtained, even in the relatively nonpolar solvent CH2Cl2.The TiCl4-mediated reactions of cyclic acetals 18c, 18t, 25, and 28 with silyl enol ether 5 show that in these systems the substitution does not occur by the SN2 mechanism.
