945406-20-2

Upstream product

• 917-54-4 methyllithium 
• 343239-55-4 4-[(1S)-1,5-dimethylhex-4-enyl]cyclohex-2-en-1-one 
• 75-24-1 trimethylaluminum 

Downstream Products

• 1443428-08-7 (3S,6S,7S)-10,11-epoxy-bisaboladiene-3-ol 
• 107175-68-8 ent-7-epi-zingiberene 

Relevant academic research and scientific papers

Expedient synthesis of bisabolenol stink bug pheromones via stereodefined cyclohex-2-enones

We recently synthesized all stereoisomers of 1,10-bisaboladien-3-ol and 10,11-epoxy-1-bisabolen-3-ol, including three stink bug pheromones, via a rhodium-catalyzed asymmetric addition of trimethylaluminum to diastereomeric mixtures of cyclohex-2-enones. However, yields of trans isomers were low, and scaling reactions using expensive catalysts were cumbersome. Now we describe a new synthesis of bisabolenol stink bug pheromones via (S)- and (R)-4-((R)-6-methylhept-5-en-2-yl)cyclohex-2-enones prepared by enantioselective Michael additions of methyl vinyl ketone to (S)- and (R)-citronellals and lithium hydroxide monohydrate-catalyzed stereoselective cyclizations of intermediate ketoaldehydes. Addition of methyllithium to these enones provided cis- and trans-1,10-bisaboladien-3-ols, which were separated by chromatography on silica and further converted to 10,11-epoxy-1-bisabolen-3-ols. Thus, we developed more convenient syntheses of pheromones of the rice stink bug, the harlequin bug, and brown marmorated stink bug.

Discovery of the aggregation pheromone of the brown marmorated stink bug (Halyomorpha halys) through the creation of stereoisomeric libraries of 1-bisabolen-3-ols

We describe a novel and straightforward route to all stereoisomers of 1,10-bisaboladien-3-ol and 10,11-epoxy-1-bisabolen-3-ol via the rhodium-catalyzed asymmetric addition of trimethylaluminum to diastereomeric mixtures of cyclohex-2-enones 1 and 2. The detailed stereoisomeric structures of many natural sesquiterpenes with the bisabolane skeleton were previously unknown because of the absence of stereoselective syntheses of individual stereoisomers. Several of the bisabolenols are pheromones of economically important pentatomid bug species. Single-crystal X-ray crystallography of underivatized triol 13 provided unequivocal proof of the relative and absolute configurations. Two of the epoxides, (3S,6S,7R,10S)-10,11-epoxy-1-bisabolen-3-ol (3) and (3R,6S,7R,10S)-10,11-epoxy-1-bisabolen-3-ol (4), were identified as the main components of a male-produced aggregation pheromone of the brown marmorated stink bug, Halyomorpha halys, using GC analyses on enantioselective columns. Both compounds attracted female, male, and nymphal H. halys in field trials. Moreover, mixtures of stereoisomers containing epoxides 3 and 4 were also attractive to H. halys, signifying that the presence of additional stereoisomers did not hinder attraction of H. halys and relatively inexpensive mixtures can be used in monitoring, as well as control strategies. H. halys is a polyphagous invasive species in the U.S. and Europe that causes severe injury to fruit, vegetables, and field crops and is also a serious nuisance pest.

COMPOSITIONS AND METHODS TO ATTRACT THE BROWN MARMORATED STINK BUG (BMSB), HALYOMORPHA HALYS

A composition (useful for attracting Halyomorpha halys) containing (3R,6R,7R,10S)-10,11-epoxy-1-bisabolen-3-ol, (3R,6R,7R,10R)-10,11-epoxy-1-bisabolen-3-ol, (3S,6S,7R,10S)-10,11-epoxy-1-bisabolen-3-ol, (3S,6S,7R,10R)-10,11-epoxy-1-bisabolen-3-ol, and optionally a carrier material or carrier. The composition may also contain (3R,6S,7R,10S)-10,11-epoxy-1-bisabolen-3-ol, (3R,6S,7R,10R)-10,11-epoxy-1-bisabolen-3-ol, (3S,6R,7R,10S)-10,11-epoxy-1-bisabolen-3-ol, (3S,6R,7R,10R)-10,11-epoxy-1-bisabolen-3-ol where the composition contains a 3:1 ratio of cis-epoxybisabolenols : trans-epoxybisabolenols produced from (R)-citronellal. These compositions were based on the newly discovered aggregation pheromone components: (3S,6S,7R,10S)-10,11-epoxy-1-bisabolen-3-ol and (3R,6S,7R,10S)-10,11-epoxy-1-bisabolen-3-ol. The composition may also contain methyl (2E,4E,6Z)-decatrieonate. Also a method for attracting Halyomorpha halys to an object or area, involving treating said object or area with a Halyomorpha halys attracting composition containing a Halyomorpha halys attracting effective amount of the composition.