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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

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journal contribution
posted on 03.10.2014, 00:00 by Ali M. Al Hazmi, Nadeem S. Sheikh, Carole J. R. Bataille, Azzam A. M. Al-Hadedi, Sam V. Watkin, Tim J. Luker, Nicholas P. Camp, Richard C. D. Brown
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 (dr ∼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.