σ- versus π-Activation of Alkynyl Benzoates Using B(C(6)F(5))(3)

We have prepared a range of alkynyl benzoates in high yields and have investigated their reactivities with the strong Lewis acid B(C(6)F(5))(3). In such molecules both σ-activation of the carbonyl and π-activation of the alkyne are possible. In contrast to the reactivity of propargyl esters with B(C(6)F(5))(3) which proceed via 1,2-addition of the ester and B(C(6)F(5))(3) across the alkyne, the inclusion of an additional CH(2) spacer switches off the intramolecular cyclization and selective σ-activation of the carbonyl group is observed through adduct formation. This change in reactivity appears due to the instability of the species which would be formed through B(C(6)F(5))(3) activation of the alkyne.