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).

Hydrocarbon Components of the Yellow Headed Spruce Sawfly Sex Pheromone. A Series of (Z,Z)-9,19-Dienes. J. Chem. Ecol. 8, 95-114 (1982). 

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. 

The importance of the three stereogenic centers became evident as two of the stereoisomers [(2S,3S,7S) and (2S,3R,7R)] were recognized early as sex pheromones and that other enantiomers and diastereoisomers were often found to be inhibitory to the attractive response. Recently, the sawfly pheromone field has undergone a major advance with the recognition that several sawfly species synthesize and utilize sex pheromones of different structural types than the 3,7-dimethylpentadecan-2-ols. Shorter and longer chain lengths (undecan-2-ols 2 and tridecan-2-ols 3) and an additional methyl group in position 9 or 11 (4 and 5) characterize these new pheromone discoveries (Fig. 1). With an ad-... 

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. 

The propionate ester of 3,7,ll-trimethyl-2-tridecanol is a female sex pheromone of the minor sawfly Microdiprion pallipes [36]. Pinesaw fly sex pheromones can be used as a... 

Insects can also manipulate plant chemistry for purposes other than nutrition. For example, Pontania spp. sawflies increase the tannin content preferentially at the outer gall regions for defensive purposes,and the gall wasp Anistrophus rufis modifies the pattern of volatile terpenes emitted hy Asteraceae host plants to generate sex pheromone-like substances that serve as localization cues for male wasps. ... 

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-... 

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. 

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. 

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