Synthesis of [16,16,16-2H3] 11-hexadecynoic acid and [15,15,16,16,16-2H5] (Z,Z)-11,13-hexadecadienoic acid and their use as tracers in a key step of the sex pheromone biosynthesis of the processionary moth.

A multifunctional desaturase involved in the biosynthesis of the processionary moth sex pheromone

“…The processionary moth sex pheromone, (Z)-13-hexadecen-11-ynyl acetate, is biosynthesized from palmitic acid by sequential ⌬ 11 desaturation, ⌬ 11 acetylenation and ⌬ 13 desaturation, followed by final reduction and acetylation (13)(14)(15)(16)(17). This biosynthetic pathway suggested that three different desaturases were involved in the process.…”

“…This compound is further ⌬ 13 desaturated to give the enynoic immediate pheromone precursor ( Fig. 1), which is finally reduced and acetylated (13)(14)(15)(16)(17).…”

Biosynthesis and function of polyacetylenes and allied natural products

“…The pheromone pathway is regulated by the Pheromone Biosynthesis Activating Neuropeptide (PBAN), whose presence allows the conversion of the enynoic acid to the acetylated pheromone [91]. While labeling experiments have shown that Thaumetopoea pityocampa Δ 11 -desaturates 16:0, installs the acetylenic bond, and then dehydrogenates C-13:14 in strict sequence prior to the modifications at the carboxylate group, Thaumetopoea processionea was found to produce only the corresponding 11,13-dienyl esters [92,93]. Formation of the dienyl acetate in T.…”

Efficient Syntheses of Traumatic Lactone and Rhizobialide

“…After evaporation, crude rac-12 [20] (94 %N MR yield, determined by 1 HNMR of crude product by using 1,3,5-trimethylbenzene as internal standard) was afforded, which was submitted to the next step without purification. The mixture was stirred under H 2 (25 atm) at RT for 30 ha nd then filtered through as hort column of silica gel (EtOAc, 15 mL 4).…”

“…The combined organic layers were washed with brine and dried over anhydrous Na 2 SO 4 .A fter filtration and concentration, the residue was purified by chromatography on silica gel (petroleum ether (60-90 8C)/ethyl acetate, 10:1 (550 mL) to 8:1( 450 mL) to 5:1( 600 mL) to 3:1 (480 mL) to 1:1( 600 mL)) to afford am ixture of rhizobialide 2 and lactonyl ester 15 (66.4 mg, 1:1( determined by 1 HNMR spectroscopy), 22 % ( 2), 22 %( 15)), as well as traumatic lactone rac-1 (49.0 mg, 43 %). Synthesis of 5-(8-hydroxyoctyl)dihydro-2(3H)-furanone rac-12 (zj-8-143) Following typical Procedure V:T he reaction of alkene rac-11 (0.4532 g, 1.5 mmol) in EtOAc (9 mL) and Pd/C (10 %o nC ,d ry, 0.0799 g, 0.075 mmol) for 30 h, after purification by column chromatography (petroleum ether (60-90 8C)/ethyl acetate, 8:1 (270 mL) to 5:1( 360 mL) to 3:1( 400 mL) to 1.5:1 (500 mL)), afforded lactone rac-12 [20] 4, 81.0, 62.5, 35.3, 32.5, 29.2, 29.1, 29.0, 28.7, 27.8, 25.5, 25.0 ppm;I R( neat): ñ = 3406, 3342, 2988, 2935, 2853, 1755, 1470, 1356, 1234, 1197, 1181, 1127, 1058, 1026, 1009 Following typical procedure I:T he reaction of Fe(NO 3 ) 3 ·9 H 2 O (0.0489 g, 0.12 mmol, 99 %), NaCl (0.0071 g, 0.12 mmol), TEMPO (0.0191 g, 0.12 mmol, 98 %), CH 2 Cl 2 (3 mL), and alcohol rac-12 (0.2570 g, 1.2 mmol) in DCE (3 mL) at RT,a fter purification by column chromatography (petroleum ether (60-90 8C)/ethyl acetate, 8:1( 360 mL) to 5:1( 600 mL 2)), afforded ketone rac-16 [16a] (0.1848 g, 73 %) as an oil. 1 202.5, 177.0, 80.6, 43.3, 35.0, 28.7, 28.6, 28.5, 28.4, 27.5, 24.7, 21.5 ppm;I R( neat): ñ = 2931, 2857, 2723, 1774, 1723, 1462, 1421, 1390, 1354, 1284, 1219, 1180, 1121, 1018 Synthesis of rac-rhizobialide (zj-8-150, zj-8-153) Typical procedure IX: [21] To ad ry Schlenk tube were added n-C 6 H 13 MgBr (1.05 mL, 1.05 mmol, 1.0 m in THF) and THF (3 mL) under an itrogen atmosphere.…”