We sought to develop true, one-pot rearrangement reactions of primary allylic silanol substrates. Our investigations were motivated by both fundamental and applied considerations. Our laboratory has furnished the only precedent for the rearrangements of silanol substrates, and we thus felt that further investigation of this fascinating substrate class was warranted. Furthermore, organomercurial compounds are known valuable synthons (Scheme 2). The C-Hg bond is a highly unusual organometallic linkage with essentially covalent character. C-Hg bonds are known precursors for carbon-centered radicals and can be facilely transformed into C-C, C-O, and C-I bonds. We wondered if we could build on our previous work to furnish technology for a rearrangement-remercuration of primary allylic silanols into organomercurial synthons. Here, we are pleased to report that, though careful control of reaction conditions, allylic silanols can be rearranged into 5-membered silanediol organomercurial heterocycles or into linear organomercurial ketones (Scheme 1). To our knowledge, no analogous transformation exists in the literature. Our initial explorations began with (E)-di-tert-butyl(hex-2en-1-yloxy)silanol (Table ), readily available from condensation of commercially available trans-2-hexen-1-ol with di-tertbutylsilylbis(trifluoromethanesulfonate). With 1.5 equivalents of Hg(OTf)2 in THF at 0 °C, we were surprised and pleased to isolate approximately 14% of unusual organomercurial ketone product 28 (Table , Entry 1). Dropping the temperature to -10 °C decreased the yield of 28 to 10% and further decreasing the temperature to -40 °C completely precluded its formation (Table , Entries 2-3). Increasing the temperature to 10 °C was slightly beneficial however (Table , Entry 4). NaHCO3, CCl3CO2Na, or CH3CO2Na as base additives were invariably deleterious (Table , Entries 5-7). A dramatic improvement came with employing CF3CO2Na as a base additive and allowing the reaction temperature to warm to 23 °C over a period of 16 hours (Table , Entry 8). With CF3CO2Na, switching the reaction solvent from THF to NO2Me and keeping the temperature at 0 °C for 2 hours allowed for still greater product formation (Table , Entry 9). We selected the conditions in Please do not adjust margins Please do not adjust margins