Scalable synthesis of the pink gypsy moth <i>Lymantria mathura</i> sex pheromone (–)-mathuralure

MowatJeffrey,; SeniorJames,; KangBaldip,; BrittonRobert,

doi:10.1139/cjc-2012-0376

Cited by 5 publications

(7 citation statements)

References 29 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Mori et al 50 proved by total synthesis that acoradiene (55) was the major component of the maleproduced aggregation pheromone arising from Gnatocerus cornutus (broad-horned flour beetle). Starting from the chiral pool, pulegone (56), through a series of steps that can be summarized as ring contraction (i.e. 57) followed by alkylation to incorporate a linear 4 carbon unit (i.e.…”

Section: Figure 12mentioning

confidence: 99%

Chromatography with silver nitrate: part 2

Mander

Williams

2016

Tetrahedron

View full text Add to dashboard Cite

Silver nitrate chromatography, or argentation chromatography, which was first discovered in the 1960's, has seen wide application to the separation and purification of alkenes, and other π-donors. Herein, a review covering the years 2001-2015 has been complied demonstrating that this technique is still in high demand for problematic separation of unsaturated organic compounds of increasing complexity.

show abstract

Section: Figure 12mentioning

confidence: 99%

Chromatography with silver nitrate: part 2

Mander

Williams

2016

Tetrahedron

View full text Add to dashboard Cite

show abstract

“…The preparation of diyne 8 was performed as previously reported. 11 Unfortunately, attempted Lindlar reduction of the internal alkyne in 8 gave no conversion to wanted 9 . However, the stereoselective Z -reduction of the internal alkyne was successfully achieved with P-2 nickel boride (P-2 Ni), 12,13 which provided 9 in 80% yield.…”

Section: Resultsmentioning

confidence: 99%

“…Next, vinyl iodide 13 was prepared from commercially available (R)-α-hydroxy-γ-butyrolactone (11), via known alcohol 12. 14 An alkyne hydrozirconation of 12, followed by treatment with iodine, furnished the vinyl iodide 13 in fair yield (Scheme 3).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…First, a synthesis of the terminal alkyne 10 from commercially available 2-pentyn-1-ol ( 6 ), Scheme , was needed. The preparation of diyne 8 was performed as previously reported . Unfortunately, attempted Lindlar reduction of the internal alkyne in 8 gave no conversion to wanted 9 .…”

Section: Resultsmentioning

confidence: 99%

“…After stirring for 15 min at room temperature, ethylenediamine (116 μL, 105 mg, 1.74 mmol) was added, and the stirring was continued for 10 min. The flask was evacuated and refilled with hydrogen gas before the skipped diyne 8 (11) was added (1.00 g, 6.09 mmol, 1.00 equiv). The reaction mixture was stirred at room temperature under hydrogen atmosphere until completion (∼4 h), then filtered through a short plug of silica gel that was washed with pentane (10 mL).…”

Section: Experimental Sectionmentioning

confidence: 99%

See 2 more Smart Citations

Synthesis of 13(R)-Hydroxy-7Z,10Z,13R,14E,16Z,19Z Docosapentaenoic Acid (13R-HDPA) and Its Biosynthetic Conversion to the 13-Series Resolvins

et al. 2016

View full text Add to dashboard Cite

Specialized pro-resolving lipid mediators are biosynthesized during the resolution phase of acute inflammation from n-3 polyunsaturated fatty acids. Recently, the isolation and identification of the four novel mediators denoted 13-series resolvins, namely RvT1 (1), RvT2 (2), RvT3 (3) and RvT4 (4) were reported, that showed potent bioactions characteristic for specialized pro-resolving lipid mediators. Herein, based on results from LC/MS-MS metabololipidomics and the stereoselective synthesis of 13(R)-hydroxy-7Z,10Z,13R,14E,16Z,19Z docosapentaenoic acid (13R-HDPA, 5), we provide direct evidence that the four novel mediators 1–4 are all biosynthesized from 5. The UV and LC/MS-MS results from synthetic 13R-HDPA (5) matched those from endogenously and biosynthetically produced material obtained from in vivo infectious exudates, endothelial cells and human recombinant COX-2 enzyme. Stereochemically pure 5 was obtained with the use of a chiral pool starting material that installed the configuration at the C-13 atom as R. Two stereoselective Z-Wittig reactions and two Z-selective reductions of internal alkynes afforded the geometrically pure alkene moieties in 5. Incubation of 5 with isolated human neutrophils gave RvTs 1–4. Together, the results herein provide new knowledge on the biosynthetic pathways and the enzymatic origin of RvTs 1–4.

show abstract

Route Scouting towards a Methyl Jasmonate Precursor

Chapuis¹,

Walther²,

Robvieux³

et al. 2016

Helvetica Chimica Acta

View full text Add to dashboard Cite

For the synthesis of methyl jasmonate (1), via the strategic intermediates 3, 4, and 6a, we constructed a synthetic network via the diverse intermediates 7–10, 13, 14, 17, and 18. This allowed us to compare the efficiency of more than 20 novel routes. The most productive pathway with a total yield of 38% is represented by the sequence→5a→5m→13b→13a→6a→4 and proceeds via sequential bromination, basic elimination, decarbomethoxylation, isomerization, and finally Lindlar hydrogenation. The shortest selective way, 2a→[(E,E)‐12b]→3→4, is a two‐pot sequence using a modification of Naef's method, based on an aldol condensation between inexpensive cyclopentanone (2a) and crotonaldehyde, with in situ CoreyChaykovsky cyclopropanation under phase transfer conditions. The key intermediate 3 was then simply pyrolyzed to afford 4 in 27% total yield. The alternative isomerization method via the six‐step deviation→5a→5c→8c→13a→6a→4 was longer, although more efficient, with a total yield of 32%. Alternatively, a yield of 34% was obtained via the five‐step sequence→5a→5c→2h→2i→4. Another favored six‐step pathway,→5a→5c→2h→17a→14a→4 afforded the target compound in 35% total yield.

show abstract

Scalable synthesis of the pink gypsy moth Lymantria mathura sex pheromone (–)-mathuralure

Cited by 5 publications

References 29 publications

Chromatography with silver nitrate: part 2

Chromatography with silver nitrate: part 2

Synthesis of 13(R)-Hydroxy-7Z,10Z,13R,14E,16Z,19Z Docosapentaenoic Acid (13R-HDPA) and Its Biosynthetic Conversion to the 13-Series Resolvins

Route Scouting towards a Methyl Jasmonate Precursor

Contact Info

Product

Resources

About