52341-11-4Relevant academic research and scientific papers
Synthesis of S-(+)-methoprene
Odinokov, V. N.,Ishmuratov, G. Yu.,Kharisov, R. Ya.,Serebryakov, E. P.,Tolstikov, G. A.
, p. 98 - 99 (2007/10/02)
An optically active juvenile hormone analogue, S-(+)-methoprene (1), is synthesized in six steps from technical grade S-(+)-3,7-dimethyl-1,6-octadiene (''(+)-dihydromyrcene'', e.e. ca. 50percent) by a novel procedure which begins with selective hydroalumination-oxidation to give S-(-)-citronellol.This alcohol is oxidized to give S-(-)-citronellal which on reaction with allylmagnesium chloride affords 6S,10-dimethyl-1,9-undecadien-4R/S-ol (5).Smidt-Moiseev oxygenation of 5 followed by dehydration leads to 6S,10-dimethyl-3E,9-undecadien-2-one.The latter on treatment with isopropoxyethynylmagnesium bromide is transformed into isopropyl 3,7S,11-trimethyl-2E/Z,4E,10-dodecatrienoate which upon Brown solvomercuration-reduction in MeOH gives 1 in 14percent overall yield.
On the stereochemistry of the Horner-Emmons reaction between 3-functionally substituted 2-methyl-2-propenylphosphonates and aliphatic aldehydes 7. Quaternary ammonium phase transfer catalysts in a stereoselective synthesis of esters of 3-methyl-2E,4E-alkadienoic acids
Kryshtal', G. V.,Zhdankina, G. M.,Serebryakov, E. P.
, p. 1048 - 1052 (2007/10/02)
The reaction of diethyl 3-ethoxycarbonyl-2-methyl-2-propenylphosphonate (1a) with 3-methylbutanal (2) in heterogeneous MOH (solid)-behzene systems in the presence of 5-10 mol.percent of benzyltriethylammonium chloride (BTEAC) gives the reaction product (3) with a higher, for M = K, or lower, for M = Li, ratio of 2E,4E- and 2Z,4E-stereoisomers than that observed in the absence of BTEAC.Tetrabutylammonium bromide (TBAB) as a catalyst of the reaction 1a + 2 -> 3 in the system KOH (solid) - wet benzene leads to a higher : ratio than BTEAC; this ratio grows from 44:56 without TBAB to 80:20 at 100 mol.percent of TBAB.In the latter case...
TERPENES IN ORGANIC SYNTHESIS. 13. SYNTHESIS OF S-(+)-METHOPRENE FROM (+)-&β-CITRONELLENE
Serebryakov, E. P.,Zhdankina, G. M.,Kryshtal', G. V.,Mavrov, M. V.,Khao, Nguen Kong
, p. 739 - 743 (2007/10/02)
S-(+)-Methoprene (I) was synthesized from (+)-β-citronellene (III) with an optical purity of about 50percent.The optical purity of the key intermediate, S-(-)-7-methoxy-3,7-dimethyl-1-octanol (IV), can be increased by fractional crystallization of the optical active acid phthalate salt (VI) followed by hydrolytic crystallization of the alcohol (IV).The yield of (I) at the final synthetic stage can be increased by use of interphase catalysis.S-(+)-Methoprene has a higher morphogenetic activity than the racemic form.
OZONOLYSIS OF ALKENES AND THE REACTION OF POLYFUNCTIONAL COMPOUNDS. XXXVIII. SYNTHESIS OF ISOPROPYL 3,7,11-TRIMETHYL-11-METHOXY-2E-DODECADIENOATE
Odinokov, V. N.,Kukovinets, O. S.,Zainullin, R. A.,Tolstikov, G. A.
, p. 650 - 653 (2007/10/02)
Isopropyl 3,7,11-trimethyl-11-methoxy-2ξ-dodecenoate was obtained by the ozonolysis of 1,5-dimethyl-1-cyclo-octene followed by transformations of the 4-methyl-1,1-dimethoxy-8-oxononane, including ethoxycarbonylmethylenation at the keto group, reaction of the aldehyde group with isopropylidenetriphenylphosphorane, and methoxylation.Allylic bromination of the product, followed by dehydrobromination, gave isopropyl 3,7,11-trimethyl-11-methoxy-2,4-dodecadienoate in the form of a mixture (82:18) of the 2E,4E- and 2Z,4E-isomers (yield calculated on the initial cyclooctene 15percent).The individual 2E,4E-isomer was isolated by preparative high-performance chromatography.
Stereocontrolled Synthesis of the Insect Growth Regulators - Alkyl (2E,4E)-Dodecadienoates
Novak, Lajos,Rohaly, Janos,Kolonits, Pal,Fekete, Jenoe,Varjas, Laszlo,Szantay, Csaba
, p. 1173 - 1182 (2007/10/02)
The title compounds 1 and 16 were synthesized by condensation of the dianions of β-keto esters 5 and 11 with aldehydes 4, and lithium dialkylcuprate addition to the enol acetate or enol phosphate of unsaturated β-keto esters 8 and 15.The (2E,4E)-dodecadienoate derivatives 1 and 16 were formed in a stereoselective manner.
