The total synthesis of (+)-petromyroxol ( 1 ) and its seven diastereomers including the (−)- iso -petromyroxol ( 2 ) is described. The employed strategy involves the use of easily available C5-epimeric epoxides 5 and 5′ and nonselective anomeric C1-allylation, proceeding with or without inversion at C2, thereby giving the possibility of synthesizing all possible diastereomers. Extensive two-dimensional (2D) NMR analyses of all eight diastereomers have been carried out to assign the chemical shifts of the central carbons and the corresponding attached hydrogens and to learn how the C/H-chemical shifts of the tetrahydrofuran ring were influenced by the adjacent centers.

A highly diastereoselective total synthesis of several bis-THF C15 acetogenin class of natural products: chloroenyne from Laurencia Majuscula, laurendecumenyne B laurefurenynes A/B and synthesis of an advanced intermediate reported in the earlier total synthesis of (E/Z)-elatenynes (formal Synthesis) are described. The salient features in the synthesis include epoxide opening, Birch reduction, Sharpless asymmetric dihydroxylation-cycloetherification, SN2 halogenation and a (relay-) cross-metathesis.