Protecting-group-directed stereodivergent Tsuji-Trost cyclization: total synthesis of oxylipids and (+)-petromyroxol.

A stereodivergent protecting-group-directed Tsuji-Trost cyclization for efficient synthesis of both 2,5- cis - and 2,5- trans -disubstituted-THF scaffolds has been realized. The presence of a β- O -silyl group in allyl acetate results in cis -2,5-disubstituted-3-oxygenated THF in a good up to 9 : 1 dr. Alternatively, when the free OH at the β-position is available for acetate co-ordination, it gives a trans -2,5-disubstituted-3-hydroxy THF scaffold almost as a single diastereomer (up to 1 : 0 dr). The THF scaffolds synthesized were carried forward in the total synthesis of oxylipids and (+)-petromyroxol.