71899-37-1

The present disclosure provides pheromone compositions. In some aspects, the compositions taught herein comprise a pheromone chemically corresponding to the pheromone naturally produced by a given insect, along with at least one positional isomer of said pheromone. In various aspects, pheromone compositions of the present disclosure are able to modulate the response of the insect based on the ratio of natural pheromone to its positional isomer.

In certain aspects, the present invention provides methods for producing terminally hydroxylated alkenes and alkynes by contacting an unsaturated or saturated hydrocarbon substrate with a hydroxylase enzyme. Exemplary terminal hydroxylases useful for carrying out the methods of the invention exhibit strong selectivity towards one terminal carbon of a hydrocarbon substrate and include, but are not limited to, non-heme diiron alkane monooxygenases, cytochromes P450 (e.g., cytochromes P450 of the CYP52 and CYP153 family), as well as long chain alkane hydroxylases. In some embodiments, the terminally hydroxylated alkene or alkyne is further converted to a terminal alkenal. In certain embodiments, terminally hydroxylated alkenes and alkynes are useful as insect pheromones which modify insect behavior. In other embodiments, terminally hydroxylated alkenes and alkynes are useful intermediates for producing pheromones via acetylation or oxidation of the alcohol moiety.

Alkynes may be easily alkylated by sequential treatment with n-BuLi followed by an alkyl halide in THF. Primary iodides give excellent yields (75-99%) as do bromides in the presence of catalytic amounts of Bu4NI or NaI; in the absence of an iodide source, bromides react poorly. This method offers advantages over existing methods which use HMPA or NH3 as co-solvents.

Various aliphatic organoboron derivatives were transmetalated to the corresponding dialkylzincs using diethyl- or dimethyl-zinc. This allows an access to zinc reagents not readily available by standard methods. Didecylzinc obtained by this method adds with good enantioselectivity (83% ee) to PhCHO in the presence of catalytic amounts of (1R, 2R)-1,2-bis-(trifluorosulfonamido)cyclohexane.

The transfer reaction induced by iodination of lithium alkynyl "ate" complexes of organoboranes represents a novel route to unsymmetrical alkynes.Several potential "blocking" groups were examined in order to achieve the selective migration of one primary alkyl group and thereby increase the efficiency of this process.Best results were obtained with the combined use of the thexyl and methoxy moieties as "blocking" groups in this reaction.The required thexylalkylborinate intermediates were conveniently prepared in high yield from thexylchloroborane via hydroboration and methanolysis.Subsequent complexation with an appropriate lithium alkyne, followed by iodination, produced the desired unsymmetrical alkyne in high yield.Minimum amounts of the product resulting from competitive migration of the thexyl group were observed.Under these conditions, an efficient utilization of a primary alkyl group in this transfer reaction is achieved.Furthermore, the high tolerance of thexylchloroborane toward many functional groups and its high regioselectivity in terminal alkene hydroboration produces intermediates that are particularly useful for the synthesis of insect pheromones and not readily accessible via conventional organometallic procedures.

Three types of coupling reactions of gem-difluoroolefins derived easily from aldehydes with lithium reagents (R'Li and R'2NLi) are described which constitute the facile procedures for conversions of aldehydes (RCHO) to amides (RCH2CONR'2), acetylenes (RCCR'), and ketones (RCH2COR').