Regioselective Isomerisation of Highly Substituted 1-Methylenecyclohexenepoxides to the Corresponding Allylic Alcohols. Influence of the Base and of the Protecting Groups

Summary.

Highly substituted 1-methylenecyclohexenepoxides 3, useful building blocks for a projected synthesis of wailupemycin A (1), were synthesized from (R)-carvone in eight synthetic steps in 23–40% overall yield. The regioselectivity of the subsequent isomerisation to the corresponding allylic alcohols was shown to depend on the basicity of the reagent and on the bulkiness of the protecting groups existing in 3. With diethylaluminum 2,2,6,6-tetramethylpiperidid (DATMP), secondary allylic alcohols 5 were formed exclusively. With strong bases such as a mixture of lithium di-iso-propylamide and potassium tert-butoxide (LIDAKOR), the tertiary allylic alcohol 6 was obtained as predominant product.