Queen bee substance synthesis

This reaction provides a useful way of introducing a double bond next to a carbonyl group. Here it is in a synthesis by Barry Trost of the Queen Bee Substance (the compound fed by the workers to those bee larvae destined to become queens). The compound is also a pheromone of the termite and is used to trap these destructive pests. Trost started with the monoester of a dicarboxylic acid, which he converted to a methyl ketone by reacting the acyl chloride with a cuprate. The ketone was then protected as a dioxolane derivative to prevent it enolizing, and the sulfur was introduced by reacting the enolate of the ester with the sulfur electrophile MeSSMe. 

Dicarboxylic esters are used to prepare polyesters and polyamides. The residual double bonds permit cross-linking of the polymer chains. Cross metathesis of methyl oleate with excess ethene affords methyl 9-decenoate, a key intermediate in the synthesis of queen bee substance , a honey bee pheromone. 

In one synthesis of the queen substance of honey bees (9) (cf p ) the double bond is derived from an... 

Callow R. K. and Johnson N. C. (1960) The chemical constitution and synthesis of queen substance of honeybees (Apis mellifera L.). Bee World 41, 152-153. 

The dimerization of butadiene is a useful method for the synthesis of various natural products. Pellitorine, which is an insecticidal compound isolated from Amcydkm pyrethrum roots, queen substances, which are well-known honey bee pheromones, ds-dvetone, which is a naturally occurring unique symmetric 17-manbered cyclic ketone, and recifeiolide, which consists of a 12-membered lactone firamwork, can readily be synthesized from butadiene dimers. 

The same telomer was used by Baker et al. to synthesize the dimethyl-pentadecari 2-ol, the pheromone of the pine sawfly [16]. Also the queen substance, a well-known honey bee pheromone, is formed starting from the malonate telomer, which has exactly the right carbon number and a suitable functionality for a facile synthesis of this natural product (Equation 16) [17]. 

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