Prins Reaction - Variations

Variations

Many variations of the Prins reaction exist because it lends itself easily to cyclization reactions and because it is possible to capture the oxo-carbenium ion with a large array of nucleophiles. The halo-Prins reaction is one such modification with replacement of protic acids and water by lewis acids such as stannic chloride and boron tribromide. The halogen is now the nucleophile recombining with the carbocation. The cyclization of certain allyl pulegones in scheme 7 with titanium tetrachloride in dichloromethane at -78°C gives access to the decalin skeleton with the hydroxyl group and chlorine group predominantly in cis configuration (91% cis). This observed cis diastereoselectivity is due to the intermediate formation of a trichlorotitanium alkoxide making possible an easy delivery of chlorine to the carbocation ion from the same face. The trans isomer is preferred (98% cis) when the switch is made to a tin tetrachloride reaction at room temperature.

The Prins-pinacol reaction is a cascade reaction of a Prins reaction and a pinacol rearrangement. The carbonyl group in the reactant in scheme 8 is masked as a dimethyl acetal and the hydroxyl group is masked as a triisopropylsilyl ether (TIPS). With lewis acid stannic chloride the oxonium ion is activated and the pinacol rearrangement of the resulting Prins intermediate results in ring contraction and referral of the positive charge to the TIPS ether which eventually forms an aldehyde group in the final product as a mixture of cis and trans isomers with modest diastereoselectivity.