Lewis acidity drives an array of organic transformations. Trialkylsilyl groups have traditionally been used as protecting groups, but can also provide Lewis acid sites for non-covalent interactions. The Adler group at Northern Illinois University examines the Lewis acidity of molecules of trialkyloxysilanes using structurally well-defined ortho-substituted carbonylbenzene scaffolds. In collaborating with this group, we have computationally examined a series of o-silyloxybenzaldehydes 1, 2-C6H4[C(=O)H](OSiR3), o-silyloxyacetophenones 1, 2-C6H4[C(=O)Me](OSiR3), and o, o-disilyloxybenzaldehydes 1, 2, 6-C6H4[C(=O)H](OSiR3)2 (R = Me, i-Pr). Energies of conformers and systems with differing R groups provide insight into the substituent-dependence of the acidities of the silicon centers and their potential to drive other reactions.We have also examined o, o-(silyloxy)(different silyloxy)acetophenones 1, 2, 6-C6H4[C(=O)Me](OSiR3)(OSiR'3). The silicon-carbonyl oxygen interactions were strong enough to impart ring formation through Lewis acid-base interaction in cases when R was significantly electron withdrawing (R = F, CF3).

Computational studies of silicon Lewis acidity in <i>ortho</i>-substituted carbonylbenzene scaffolds

246th National Meeting (2013)

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Computational studies of silicon Lewis acidity in ortho-substituted carbonylbenzene scaffolds