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Compound 87 isolated in a trapping experiment681 undergoes a [2,3] sigmatropic rearrangement to yield a selenite ester (88). Hydrolysis of the latter gives the product allylic alcohol. This mechanism explains the formation of racemic products under certain reaction conditions, but does not fully account for (E)-allylic alcohol formation [Eq. (9.122)]. In fact, it predicts complete regio- and stereoselective formation of allylic alcohols, which is not commonly observed. Later, deuterium labeling studies 682 led to the conclusion that another pathway also exists. The preference for (E)-allylic alcohol formation is due to the steric effect in a six-membered chair transition state in the [2,3] sigmatropic migration in basic solution. In alcoholic solutions, a minor stereorandom path through a stepwise ene reaction involving carbocation formation explains decreased selectivities. A limited stereoselectivity of the ene reaction on the basis of BC-Iabeling experiments was also suggested. 683 The use of a catalytic amount of Se02 with reoxidants such as H202684 and tertBuOOH685 is a useful modification of the conventional process producing allylic alcohols in yields comparable to or better than stoichiometric Se02 alone. Cycloalkenes, however, give significant amounts of allylic tert-butyl ethers and tert-butyl peroxides. 686 Copper_catalyzed687-689 or photochemical 69o reaction of alkenes with peroxyesters, usually with tert-butyl peracetate (or tert-BuOOH in acetic acid), may be used to carry out acyloxylation or the synthesis of the corresponding allylic esters in good yields. In contrast to the oxidation with Se02, preferential formation without rearrangement of the 3-substituted esters takes place from terminal alkenes: 691

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