The addition of oxygen nucleophiles to non-activated alkenes is a synthetically valuable reaction which is typically carried out under strongly acidic conditions, and for which selective catalysts are limited. Especially asymmetric catalytic oxy-functionalizations are virtually unknown. For a few years, it appeared that several transition metal triflates and related strong lewis acids provide a handle towards selective hydroalkoxylation; However, many of the recently developed catalytic hydroalkoxylations of non-activated alkenes must be classified as �hidden Br�nsted acid catalyses� that show similar selectivities and cannot readily profit from ligand effects.Our search for metal catalysts for hydroalkoxylations under conditions, which would as much as possible exclude hidden acid catalysis, has led to the finding of aluminum alkoxides as catalysts for the cyclization of 2-allylphenol to 2-methylcoumaran under thermally forcing conditions in a microwave reactor (250 �C, 10 bar). We now report an asymmetric catalytic variant of this reaction by a new type of in situ generated chiral titanium carboxylate catalyst.

Asymmetric catalytic hydroalkoxylation of non-activated alkenes

248th National Meeting (2014)

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