Methylene-butyrolactones are readily accessed by two methodologies based on a particular ene reaction. Both methodologies have been applied to the synthesis of the northern fragment of Polycavernoside. A reverse Julia reaction was used as the key step of a new methodology towards triene frameworks ; a mechanistic study revealed the unexpected role of triflic acid in the field of metal triflates catalysed acylation of alcohols, and a new tandem Brook rearrangement-allylation sequence was developed in the viewpoint of an improved total synthesis of Polycavernoside A.

Methylene-butyrolactones are readily accessed by two methodologies based on a particular ene reaction. Both methodologies have been applied to the synthesis of the northern fragment of Polycavernoside. A reverse Julia reaction was used as the key step of a new methodology towards triene frameworks ; a mechanistic study revealed the unexpected role of triflic acid in the field of metal triflates catalysed acylation of alcohols, and a new tandem Brook rearrangement-allylation sequence was developed in the viewpoint of an improved total synthesis of Polycavernoside A.