(a) Assuming the presence of acids (AH) and bases (A¯) as needed, give a curved-arrow mechanism for the isomerization of isopentenyl pyrophosphate into dimethylallyl pyrophosphate.

(b) In some organisms, geranyl pyrophosphate is converted by hydrolysis into one of two enantiomeric tertiary alcohols:

Assuming the presence of acids (AH), bases (A¯), and water as needed, give a curved-arrow mechanism for this transformation. (Ignore stereochemistry.)

(c) Each of the stereoisomeric linalools in part (b) is converted into an epoxide A by CyP450, and the epoxide spontaneously forms the following compound B. Neglecting stereochemistry, suggest a structure for A; and, assuming the presence of H₃O⁺ and H₂O, provide a curved-arrow mechanism for the conversion of A into B.

Transcribed Image Text:

H₂C OH linalool (3R)-(-)-linalool (also called licareol; has a lily-of-the-valley scent) (3S)-(+)-linalool (also called coriandrol; has a musty herbaceous scent)