| 主权项 |
1. A method of making an insect pheromone or pheromone precursor, having one or more Z-alkenyl groups therein, comprising:
treating an alkyne of formula IA, IB, IC, or ID with a copper(I)-nitrogen heterocyclic carbene complex (“copper(I)-NHC”), which facilitates semireduction of the alkyne to a Z-alkene, a reducing agent containing at least one silicon-hydrogen bond, and a proton donor, thereby forming the insect pheromone or pheromone precursor having one or more Z-alkenyl groups; wherein IA is H3C—(CH2)a—C≡C—(CH2)b-Q, IB is H3C—(CH2)cC≡C—(CH2)d—C≡C—(CH2)e-Q, IC is H3C—(CH2)f—C≡C—C≡C—(CH2)g-Q, and ID is H3C-A-C≡C-E-Q; where functional group Q is an aldehyde, acetate, acyclic O,O′-acetal (—CH(OR′)(OR″), where R′ and R″ are, independently, C1 to C6 alkyl or cyclic alkyl), cyclic O,O′-acetal (—CHO(CH2)xO— where x=2, 3, or 4), hydroxyl, protected hydroxyl, formate, or halide (Cl, Br) group, and coefficients a-g are selected such that the alkyne has from 7 to 20 carbon atoms; and wherein in formula IA, a is 0 to 16, b is 1 to 7, and 4≦a+b≦17, provided that in the case where Q is Cl or Br, (a,b)≠(1,8); in formula IB, c is 0 to 13, d is 1 to 14, e is 1 to 14, and 2≦c+d+e≦15; in formula IC, f is 0 to 14, g is 1 to 15, and 2≦f+g≦15; and in formula ID, groups A and E are, independently, C1 to C10 alkylenyl or alkenyl, provided that at least one of A and E is an alkenyl group and the alkyne has from 7 to 20 carbon atoms. |
