Synthesis of Optically Pure (1S, 4S, 5S)-2-Pinen-4-ol (cis-Verbenol) and Its Antipode, the Pheromone ofIpsBark Beetles

Synthetic examination of incorrectly proposed structures of biomolecules

“…When one compares the sign of the optical rotation of one's sample with previous data by others, it is of utmost importance that the same solvent is used as reported by the others. In 1976, a similar example of different signs of optical rotations in different solvents was reported by Mori et al when they synthesized (1 S ,4 S ,5 S )‐ cis ‐verbenol, a component of Ips bark beetle pheromone61.…”

Stereospecific synthesis of cis-verbenol

“…To a solution of 0.50 g (3.3 mmol) of enone 2 in 50 mL of anhydrous CH 2 Cl 2 was added dropwise at-70°С in an argon flow 1.6 mL of 73% (i-Bu) 2 AlH solution in toluene, the mixture was stirred for 2 h, at the same temperature a mixture was added of 3.5 mL of THF and 3.5 mL of H 2 O, and the stirring was continued for 0.5 h. The separated precipitate was filtered off through a bed of Al 2 O 3 (5 cm), the organic layer was dried with Na 2 SO 4 and evaporated. Yield 0.47 g (92%), mp 66-67°С (70-71°С [5]), 1 H NMR spectrum was identical to previously published data [5]. 13 Physicochemical analyses were performed on the equipment of the Center of joint usage «Chemistry» of Ufa Institute of Chemistry of the Russian Academy of Sciences.…”

Synthesis of Pheromones

“…50 2) K 2 CO 3 , EtI DMF (74%, 2 steps) The important lesson is the fact that the sign of optical rotation may change by using a different solvent. 50 2) K 2 CO 3 , EtI DMF (74%, 2 steps) The important lesson is the fact that the sign of optical rotation may change by using a different solvent.…”

“…It was later found that the natural components are (1R,5S,7R)-99 and (S )-100. 50 of A to give B as the key step. Our synthesis of the enantiomers of 99 in 1986 started from the enantiomers of tartaric acid.…”