5299-11-6Relevant academic research and scientific papers
First preparation of single-enantiomer juvenile hormone III acid and (R)-juvenile hormone III-d3
Ichikawa, Akio,Takenaka, Makiko,Ono, Hiroshi
experimental part, p. 1800 - 1806 (2011/02/23)
The (R)- and (S)-enantiomers of juvenile hormone (JH) III acid [(R)-2 and (S)-2] were prepared by the hydrolysis of (R)- and (S)-JH III [(R)-1 and (S)-1], respectively. Each enantiomer of 2 was purified by preparative reversed-phase high performance liquid chromatography in a single operation. (RS)-2 was methylated with CH3I and K2CO3 in MeCN, yielding (RS)-1. (R)-JH III-d3 [(R)-3], a single-enantiomer internal standard for quantification, was prepared from (R)-2 with CD3I and K2CO3 in MeCN.
Substrate specificity for the epoxidation of terpenoids and active site topology of house fly cytochrome P450 6A1
Andersen, John F.,Walding, Jennifer K.,Evans, Philip H.,Bowers, William S.,Feyereisen, Rene
, p. 156 - 164 (2007/10/03)
Heterologous expression in Escherichia coli, purification, and reconstitution of house fly P450 6A1 and NADPH-cytochrome P450 reductase were used to study the metabolism of terpenoids. In addition to the epoxidation of cyclodiene insecticides demonstrated previously [Andersen et al. (1994) Biochemistry 33, 2171-2177], this cytochrome P450 was shown to epoxidize a variety of terpenoids such as farnesyl, geranyl, and neryl methyl esters, juvenile hormones I and III, and farnesal but not farnesol or farnesoic acid. P450 6A1 reconstituted with NADPH-cytochrome P450 reductase and phosphatidylcholine did not metabolize α-pinene, limonene, or the insect growth regulators hydroprene and methoprene. The four geometric isomers of methyl farnesoate were metabolized predominantly to the 10,11-epoxides, but also to the 6,7-epoxides and to the diepoxides. The 10,11-epoxide of methyl (2E,6E)-farnesoate was produced in a 3:1 ratio of the (10S) and (10R) enantiomers. Monoepoxides of methyl farnesoate were metabolized efficiently to the diepoxides. Methyl farnesoate epoxidation was strongly inhibited by a bulky substituted imidazole. The active site topology of P450 6A1 was studied by the reaction of the enzyme with phenyldiazene to form a phenyl-iron complex. Ferricyanide-induced in situ migration of the phenyl group showed formation of the N-phenylprotoporphyrinporphyrin IX adducts in a 17:25:33:24 ratio of the N(B):N(A):N(C):N(D) isomers. These experiments suggest that metabolism of xenobiotics by this P450, constitutively overexpressed in insecticide-resistant strains of the house fly, is not severely limited by stereochemically constrained access to the active site.
Enantioselective synthesis of juvenile hormone III in three steps from methyl farnesoate
Crispino,Sharpless
, p. 777 - 779 (2007/10/02)
The asymmetric dihydroxylation of methyl farnesoate resulted in regioselective dihydroxylation of the 10,11 olefin to give the (10S) and (10R)-(2E,6E)-10,11-dihydroxy-3,7,11-trimethyl-2,6-dodecadienoates in high ee. These diols were converted to juvenile hormone III and its enantiomer.
Regio- and Chemoselective Epoxidation of Fluorinated Monoterpenes and Sesquiterpenes by Dioxiranes
Lluch, Anna-Maria,Sanchez-Baeza, Francisco,Messeguer, Angel,Fusco, Caterina,Curci, Ruggero
, p. 6299 - 6308 (2007/10/02)
A comparative study on chemoselectivity of dimethyldioxirane (DMD) and methyl(trifluoromethyl)dioxirane (TFMD) in the epoxidation of trisubstituted C=C bonds presenting different activation in fluorinated monoterpene and sesquiterpene derivatives has been carried out.With respect to DMD, epoxidations performed with TFMD were faster under milder conditions, although high conversion yields were obtained with both reagents.In ease of epoxidation of unsaturated moieties the trend observed was: (CH3)(R1)C=CH(R2) ca. (CH3)(R1)C=CH(CH2OR) ca. (CH3)(R1)C=CF(R2) >> (CH3)(R1)C=CH(COOR) > (CF3)(R1)C=CH(R2).Results reported herein present the first example of direct epoxidation of a double bond bearing a CF3 substituent by non-biochemical means.Key Words: Epoxidation.Dimethyldioxirane; Methyl(trifluoromethyl)dioxirane.Chemoselectivity.Regioselectivity.Monoterpenes.Sesquiterpenes.
A Convenient Method for the Preparation of (+/-)Juvenile Hormone III
Rodriguez, Juan B.,Gros, Eduardo G.
, p. 93 - 95 (2007/10/02)
Following a different approach methyl (2E,6E)-farnesoate (4) was prepared in three steps from trans-geranylacetone (1).Compound 4 was regioselectively epoxidized to (+/-)juvenile hormone III.
A NEW SYNTHETIC ROUTE TO JUVENILE HORMONE KINETIC RESOLUTION OF EPOXIDES USING ORGANOALUMINUM REAGENT
Naruse, Yuji,Esaki, Toru,Yamamoto, Hisashi
, p. 1417 - 1420 (2007/10/02)
A short synthetic route to C16-juvenile hormone is described which depends on new oxirane ring opening methodology and which also involves the joining of intermediate 8 and 12 in a one flask operation to construct the sesquiterpene structure.
KINETIC RESOLUTION OF EPOXIDES BY CHIRAL ORGANOALUMINIUM CALTALYST SHORT SYNTHESIS OF (-)-C16 JUVENILE HORMONE
Naruse, Yuji,Esaki, Toru,Yamamoto,Hisashi
, p. 4747 - 4756 (2007/10/02)
The use of chiral organoaluminium reagent as a catalyst to resolve simple ketoepoxides is explored.The optically pure ketoepoxide 10 was recovered after 80percent conversion.The recovered pure epoxides is a useful chiral building block in the synthesis of
ON THE COHERENCE OF INCORPORATION OF THE FLUOROVINYL MOIETY INTO BIOACTIVE ORGANIC COMPOUNDS. SYNTHESIS OF AN INSECT JUVENILE HORMONE III FLUORINATED ANALOG.
Camps, F.,Messeguer, A.,Sanchez, Francisco-Jose
, p. 5161 - 5168 (2007/10/02)
An insect juvenile hormone fluoroanalog, methyl 10-fluoro-10,11-epoxyfarnesoate (9), has been prepared, using tandem Claisen-Cope rearrangements on fluorovinyl intermediate 1 as a crucial step.Along this synthesis chemical and spectral data have been obtained that might question some applications of fluorovinyl derivatives in the design of bioactive organic compounds.
SYNTHESIS OF BOTH THE ENANTIOMERS OF JUVENILE HORMONE III
Mori, Kenji,Mori, Hideto
, p. 4097 - 4106 (2007/10/02)
Both the enantiomers (ca.100percent e.e.) of juvenile hormone III were synthesized employing (S)-3-hydroxy-2,2-dimethylcyclohexanone as a single chiral source.
OZONOLYSIS OF ALKENES AND REACTIONS OF POLYFUNCTIONAL COMPOUNDS. XXVII. A CONVENIENT STEREOSPECIFIC SYNTHESIS OF RACEMIC INSECT JUVENILE HORMONE YUG-III
Odinokov, V. N.,Kukovinets, O. S.,Sakharova, N. I.,Tolstikov, G. A.
, p. 1075 - 1077 (2007/10/02)
A new method was developed for the stereospecific synthesis of the racemic insect juvenile hormone YUG-III, based on the selective ozonolysis of 1,5,9-trimethyl-1E,5E,9E-cyclododecatriene to 4-methyl-1,1-dimethoxy-2-oxo-4E-nonene.Subsequent coupling with isopropylidenetriphenylphosphorane and oxidation at the terminal double bond leads to methyl 3,7,11-trimethyl-10,11-epoxy-2E,6E-dodecadienoate with a total yield of 12percent.
