trans-2-Tritylcyclohexanol as a Chiral Auxiliary in Permanganate-Mediated Oxidative Cyclization of 2-Methylenehept-5-enoates: Application to the Synthesis of trans-(+)-Linalool Oxide

The permanganate-mediated oxidative cyclization of a series of 2-methylenehept-5-eneoates bearing different chiral auxiliaries was investigated, leading to the discovery of trans-2-tritylcyclohexanol (TTC) as a highly effective chiral controller for the formation of the 2,5-substituted THF diol product with high diastereoselectivity (d(r) similar to 97:3). Chiral resolution of (+/-)-TTC, prepared in one step from cyclohexene oxide, afforded (-)-(1S,2R)-TTC (er >99:1), which was applied to the synthesis of (+)-trans-(2S,5S)-linalool oxide.