Our optimized protocol was compatible with several branched alkyl (Scheme 6, Entries 1 and 7), cyclic hydrocarbon (Scheme 6, Entries 2, 5, 6, and 8), and cyclic ether (Scheme 6, Entries 3-4) substrates. We found that diol formation was quite sensitive to the branching pattern of the allylic silanol substrate (Scheme 7). For example, linear alkyl silanols decomposed rapidly into an intractable mixture of products when subjected to a combination of Hg(OTf)2 and NaHCO3 in THF at 0 °C. For such substrates (Scheme 7A and 7B), an alternate protocol of Hg(OTf)2/CF3CO2Na in THF was required to stabilize diol formation. Likewise, our standard optimized protocol failed for substrates with aromatic rings α to the alkene (Scheme 7C and 7D). For such substrates, using conditions for 6-membered cyclic silanediol formation followed by warming the reaction flask to room temperature over a period of 6 hours allowed for reasonable yields of the desired five-membered products. Crystallization of one these products, 63 (CCDC: 2084035), allowed us to establish the relative stereochemistry of the silanediol heterocycle.