Abstract
2-(3,4-Dihydro-1-naphthalen-1-yl)propan-1-ol was protected with several groups. The
reaction of these alkenol derivatives with thallium trinitrate (TTN) was then investigated.
Oxidation of the methyl, benzyl and 4-phenylbenzyl ether led to the ring contraction
product, as a single diastereomer, in reasonable yields (63-71%). The high diastereoselectivity
can be explained by coordination between thallium(III) and oxygen during the rearrangement
step. When treated with TTN under similar conditions, the acetate and benzoate derivatives
were recovered unchanged. However, using excess of the oxidant, these esters led to
indans as a 1:1 mixture of diastereomers, in 12-24% yield, together with a naphthalene
derivative, in 9-24% yield. Treatment of the silyl ether derivatives with TTN promotes
the cleavage of the protecting group, yielding the starting alkenol, which underwent
oxidation, furnishing the expected indan in 37-57%.
Key words
thallium trinitrate - ring contraction - indans - alkenols - protecting groups
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Available free of charge at http://jbcs.sbq.org.br.
