Synthesis of pheromone derivatives via Z-selective olefin metathesis

A method for synthesizing a Z-enriched fatty olefin metathesis product, the method comprising contacting an olefin metathesis reaction partner with an internal olefin in the presence of a Z-selective group 8 transition metal metathesis catalyst to form the Z-enriched fatty olefin metathesis product, wherein:

• the olefin metathesis reaction partner comprises a mixture of Z olefins and E olefins in a starting Z:E ratio,
• the fatty olefin metathesis product comprises a mixture of Z olefins and E olefins in a product Z:E ratio, and
• the product Z:E ratio is higher than the starting Z:E ratio,
• wherein:
• the fatty olefin metathesis product is an acylated alkenol of Formula I:
• the metathesis reaction partner is a compound of Formula III
• the internal olefin is a compound of Formula IV
• R1 is selected from the group consisting of H and C1-6 alkyl;
• R2 is selected from the group consisting of C1-18 alkyl and C2-18 alkenyl;
• R3 is C1-18 alkyl;
• subscript y is an integer ranging from 0 to 17;
• subscript z is an integer ranging from 0 to 17;
• and
• the Z-selective metathesis catalyst has a structure according to Formula V:
• wherein:
• M is selected from the group consisting of ruthenium and osmium;
• X and Y are independently selected from the group consisting of S and O;
• Z is selected from the group consisting of S(═O), O, N, and halogen;
• subscript m is an integer selected from 2, 4, 3, 1, and 0;
• subscript n is an integer selected from 0, 1, 2, 3, or 4;
• each Ra is independently selected from the group consisting of halogen, C1-C6 alkyl, alkoxy, aryl, and heteroaryl;
• or one Ra is taken together with an adjacent Ra to form an unsubstituted or substituted bicyclic ring, or an unsubstituted or substituted polycyclic ring;
• each Rb is independently selected from the group consisting of halogen, C1-C6 alkyl, alkoxy, aryl, and heteroaryl;
• or one Rb is taken together with an adjacent Rb to form an unsubstituted or substituted bicyclic ring, or an unsubstituted or substituted polycyclic ring;
• Rc is selected from the group consisting of hydrogen and C1-C6 alkyl;
• each Rd, Re, Rf and Rg is independently selected from the group consisting of hydrogen and C1-C6 alkyl;
• R12 and R13 are independently selected from the group consisting of 2,6-di-iso-propylphenyl, 2,4,6-tri-iso-propylphenyl, 2,6-di-adamantylphenyl, 2-iso-propyl-6-tert-butylphenyl, 2,4,6-tri-tert-butylphenyl, and 2,6-di-tert-butylphenyl;
• each R14 is independently selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl, benzyl, phenyl, and hydrogen;
• and
• R15 is selected from the group consisting of hydrogen, halogen, and C1-C6 alkyl or R15 and one R14 are taken together to form a bond, wherein the fatty olefin metathesis product is present in an amount of at least 97% Z.