Pine sawfly sex pheromones

The application of fluorous mixture synthesis (FMS) for deriving natural products and their stereoisomers was demonstrated by the total synthesis of all 16 stereoisomers of the pine sawfly sex pheromoned ... 

In the hydrogenation of p keto esters (R, R) tartaric acid gives the (R) alcohols and the (S, S) tartaric acid gives the (S) enantiomers. Raney nickel is more effective than supported nickel catalysts. It appears that the active catalyst is nickel tartrate which is adsorbed on the catalyst surface and that the sodium bromide is adsorbed on the non-chiral active sites, thus, keeping them from promoting the non-selective hydrogenations. 2,84 -pj is procedure has been used to prepare the chiral intermediate in the synthesis of the Pine Sawfly sex pheromone. ... 

Figure 13 Preparation of the pine sawflies sex pheromone components from 3-hydroxybutyric acid obtained by the hydrogenation of MAA with MRNi. (From A. Tai, Yuukigousei Kyoukaishi (J. Synthetic Organic Chemistry Japan), 58 575,2000).

Kraemer, M., Coppel, H. C., Matsumura, F., Kikukawa, T. and Mori, K. (1979) Field responses of the white pine sawfly. Neodiprion pinetum, to optical isomers of sawfly sex pheromones. Env. Ent., 8, 519-20. 

Magnusson, G. Pheromone synthesis. Preparation of er> r/ir( -3,7-dimethylpenta-decan-2-ol, the alcohol from pine sawfly sex attractant (Hymenoptera Diprionidae). Tetrahedron Lett. 1977, 2713—2716. 

The sex pheromone of the pine sawfly Diprion pint) is (25,5R, IRYiJ-dimethyltridec-2-yl acetate. This acetate was prepared from diastereomerically enriched (25, 3i , 7i )-3,7-dimethyltridecan-2-ol. 

R, 5R, 75)-3,7-dimethylpentadecan-2-ol, sex pheromone component of the pine sawfly Neodiprion sertifer, has also been synthesized enantioselectively. ... 

Hallberg E. and Lofqvist J. (1981) Morphology and ultrastructure of an intertergal pheromone gland in the abdomen of the pine sawfly Neodiprion sertifer (Insecta, Hymenoptera) a potential source of sex pheromones. Can. J. Zool. 59, 47-53. 

Species of pine sawflies in the genera Neodiprion and Pi prion secrete a sex pheromone dominated by either the acetate or propionate esters of 3,7-dimethylpentadecan-2-ol (138). Reproductive isolation of these sawflies appears to be partly related to the utilization of one or the other of these diasteriomeric esters. 

Tai, A., Imaida, M., Oda, T., and Watanabe, H. (1978) Synlliesis of optically active common precursor of sex pheromone of pine sawflies an application of enantioface-differentiating hydrogenation on modified nickel, Chem. Lett. 61-64. 

Jewett, D. M., Matsumura, F. and Coppel, H. C. (1976) Sex pheromone specificity in the pine sawflies interchange of acid moieties in an ester. Science, 192, 51-3. 

A useful application of the oxy-Cope rearrangement has been used to produce conjugated enynes [e.g. (114) - (115)]. The enyne (115) is an intermediate in a synthesis of the sex pheromone of the Pine Sawfly Neodiprion lecontei. Potassium t-butoxide in liquid ammonia has been found to be the preferred base to produce high yields of the conjugated 1-alkylthio- or l-arylthiobut-3-en-l-ynes (117). Elimination of thiols from the acetylenic disulphides (116) under these conditions completely suppresses the competing formation of cumulene or diene-sulphides. 

The sex pheromone (373) (Scheme 66) of the pine sawfly (Neodiprion lecontei) was synthesized by Kocienski and Ansell (777) as a mixture of epimers starting from 2,6-dimethylcyclohexanone. Alkylation and sub-... 

Mori, K., S. Masuda, and M. Matsui Pheromone synthesis 22. New synthesis of a stereoisomeric mixture of 3,7-dimethylpentadec-2-yl acetate, sex pheromone of pine sawflies. Agric. Biol. Chem. 42,1015—1018 (1978). 

Mori, K., S. Tamada, and M. Matsui Stereocontrolled synthesis of the four possible stereoisomers of 6 ry / ro-3,7-dimethylpentadec-2-yl acetate and propionate, the sex pheromone of the pine sawflies. Tetrahedron Letters 1978, 901—904. 

Tai, a., M. Imaida, T. Oda, and H. Watanabe Synthesis of the optically active common precursor of the sex pheromone of pine sawflies. Application of enantioface differentiating hydrogenation with modified nickel. Chemistry Lett. 1978, 61—64. 

---