Production of fatty olefin derivatives via olefin metathesis

1. A method for synthesizing a compound according to Formula VIb:

the method comprising:

acylating an alkenol according to Formula VIII

to form an acylated alkenol according to Formula IX

 and

contacting the acylated alkenol with an olefin according to Formula I

in the presence of a metathesis catalyst having a structure according to Formula 2a

thereby forming the compound of Formula VIb; wherein:

R 1 is selected from the group consisting of H, C 1-18 alkyl, and C 2-18 alkenyl;

R 2c is C 1-6 acyl,

subscript y is an integer ranging from 0 to 17;

subscript z is an integer ranging from 0 to 17;

M is Mo or W;

R 3a is aryl, heteroaryl, alkyl, or cycloalkyl, each of which is optionally substituted;

R 7a is pyrrolyl, imidazolyl, indolyl, pyrazolyl, azaindolyl, or indazolyl, each of which is optionally substituted;

R 8a is optionally substituted aryl;

R 5a is a hydrogen atom, alkyl, or alkoxy;

R 4b is a hydrogen atom, —O—(C 1-6 alkyl), —CH 2 —O—(C 1-6 alkyl), heteroalkoxy, or —N(C 1-6 alkyl) 2 ; and

R 4c and R 4d are independently a hydrogen atom, C 1-6 alkyl, C 1-6 alkoxy, a halogen atom, —NO 2 , an amide, or a sulfonamide.

2. The method of claim 1 , wherein the alkenol according to Formula VIII is formed by reducing an alkyl ester according to Formula IIb:

wherein R 2b is C 1-8 alkyl.

3. The method of claim 1 , wherein the compound of Formula VIb is selected from (Z)-7-dodecenyl acetate; (E)-7-dodecenal; (Z)-7-decenyl acetate; (Z)-7-hexadecenal; (Z)-7-hexadecenyl acetate; (Z)-7-tetradecenal; (Z)-7-tetradecenyl acetate; (Z)-7-undecenyl acetate; (Z)-10-dodecenyl acetate; (Z)-10-hexadecenyl acetate; (Z)-10-pentadecenal; (Z)-10-pentadecenyl acetate; (Z)-10-tetradecenyl acetate; (Z)-10-tridecenyl acetate; (Z)-9-dodecenal; (Z)-9-dodecenyl acetate; (Z)-9-hexadecenal; (Z)-9-hexadecenyl acetate; (Z)-9-pentadecenyl acetate; (Z)-9-tetradecenal; (Z)-9-tetradecenyl acetate; (Z)-9-tetradecenyl formate; (Z)-9-tetradecenyl nitrate; (Z)-9-tridecenyl acetate; (Z)-9-undecenyl acetate; (Z)-11-hexadecen-1-ol; (Z)-11-hexadecenal; (Z)-11-hexadecenyl acetate; (Z)-11-tetraceden-1-ol; (Z)-11-tetracedenyl acetate; (Z)-13-octadecen-1-ol; and (Z)-13-octadecenal.

4. The method of claim 1 , wherein:

R 7a is pyrrolyl, imidazolyl, pyrazolyl, azaindolyl, or indazolyl, each of which is optionally substituted; and

R 5a is a hydrogen atom.

5. The method of claim 1 , wherein R 3a is phenyl, 2,6-dichlorophenyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2-trifluoromethylphenyl, pentafluorophenyl, tert-butyl, or 1-adamantyl.

6. The method of claim 5 , wherein R 8a is:

7. The method of claim 1 , wherein R 4b is methoxy, R 4c is hydrogen, and R 4d is hydrogen.

8. The method of claim 1 , wherein the metathesis catalyst is:

9. The method of claim 1 , wherein the catalyst is present in an amount less than 0.01 mol % with respect to the olefin or to the metathesis reaction partner.

10. The method of claim 3 , wherein the compound of Formula VIb comprises at least 80% Z olefin.

11. The method claim 1 , wherein acylating the alkenol according to Formula VIII is conducted with an acylating agent selected from the group consisting of acetic anhydride and acetyl chloride.

12. The method claim 11 , wherein 1-5 molar equivalents of the acylating agent with respect to the alkenol according to Formula VIII is used.