Direct deoxygenation of active allylic alcohols via metal-free catalysis

Abstract

Direct metal-free deoxygenation of highly active allylic alcohols catalyzed by a Brønsted acid was achieved, which avoids tedious reaction steps and eliminates metal contamination. By examining a series of Brønsted acids, alcohols, reaction temperatures and so on, up to 94% yield was obtained with 10 mol% TsOH·H₂O as the catalyst and 2 equiv. of p-methylbenzyl alcohol as the reductant at 80 °C for 2 h. The system was mainly suitable for aromatic allylic alcohols, and the yield was excellent as determined via gram-scale synthesis. The main product was double bond near the side of a more electron-rich aryl group when allylic alcohols featuring different substituents at the 1 and 3 positions were used as the substrates. Deuterium-labelled experiments clearly demonstrated that the hydrogen source was the methylene of p-methylbenzyl alcohol and other control experiments indicated the existence of two ether intermediates. Interestingly, in situ hydrogen transfer of allylic benzyl ether is a key process, but kinetic isotopic effect studies (k_H/k_D = 1.28) showed that the C–H bond cleavage was not the rate-determining step. A possible mechanism involving carbocations, ether intermediates and hydrogen transfer is proposed.