- Asymmetric Synthesis of γ-Lactones. A Facile Synthesis of the Sex Pheromone of the Japanese Beetle
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The sex pheromone of the Japanese beetle, (R)-(-)-(Z)-5-tetradecen-4-olide, has been prepared in essentially 100percent optical purity by using the asymmetric reducing agent B-3-pinanyl-9-borabicyclononane to introduce chirality.
- Midland, M. Mark,Nguyen, Nhan H.
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- LIPASE-CATALYZED KINETIC RESOLUTION OF METHYL 4-HYDROXY-5-TETRADECYNOATE AND ITS APPLICATION TO A FACILE SYNTHESIS OF JAPANESE BEETLE PHEROMONE
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A kinetic resolution of methyl 4-hydroxy-5-tetradecynoate is accomplished by a lipase-catalyzed enantioselective acylation in organic solvent.Acylation of methyl 4-hydroxy-5-tetradecynoate with succinic anhydride in a organic solvent yields methyl (R)-4-succinoyloxy-5-tetradecynoate with over 90percent e.e..Furthermore, this optically active diester was converted to (R)-5-(1-decynyl)oxacyclopentane-2-one by lipase-catalyzed enantioselective lactonization which enhanced its e.e. over 99percent.The Japanese beetle pheromone (R,Z)-(-)-5-(1-decenyl)oxacyclopentan-2-one is synthesized in one step from this optically active lactone.
- Fukusaki, Eiichiro,Senda, Shuji,Nakazono, Yutaka,Omata, Tetsuo
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- Convergent and enantioselective syntheses of both enantiomers of (5Z)-tetradecen-4-olide, scarab beetle pheromones
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Japonilure and its enantiomer, that is, (R)-(-)- and (S)-(+)-(5Z)-tetradecen-4-olide, have been synthesised in satisfactory overall yields using a highly convergent procedure. In situ prepared 1-decynylethylzinc was enantioselectively coupled to isopropyl 4-oxobutanoate in the presence of (S)- or (R)-BINOL. The alkoxy-ester intermediates obtained were cyclised to the corresponding substituted γ-lactones, carrying a triple bond in the side chain. Lindlar-hydrogenation of the latter yielded the target compounds.
- Dos Santos, Alcindo A.,Francke, Wittko
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- Catalytic asymmetric synthesis of Japonilure and its enantiomer
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A mild, concise, and highly enantioselective (93% ee) synthesis of Japonilure and its enantiomer, Anomala osakana pheromone, is described. The key steps involve the asymmetric addition of methyl propionate to undec-2-ynal with a Zn-ProPhenol catalyst and the selective and partial reduction of the diynol ester to the cis-enol ester with Brown's P2-Ni catalyst, providing the first synthesis of the enol ester via semi-hydrogenating diynol ester.
- Xu, Hao,Li, Shuo-Ning,Yang, Yan-Qing,Zhou, Yun,Yang, Qian-Zhen,Bian, Qing-Hua,Zhong, Jiang-Chun,Wang, Min
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p. 1372 - 1375
(2015/01/16)
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- Synthesis of (R)-japonilure and (4R,9Z)-9-octadecen-4-olide, pheromones of the Japanese beetle and currant stem girdler
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Asymmetric total synthesis of the sex pheromones of Japanese beetle and currant stem girdler, (R)-japonilure (1) and (4R,9Z)-9-octadecen-4-olide (2), has been achieved. Copyright Taylor & Francis Group, LLC.
- Sabitha, Gowravaram,Bhaskar,Yadagiri,Yadav
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p. 2491 - 2500
(2008/02/10)
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- The preparation of nonracemic secondary α-(carbamoyloxy)alkylzinc and copper reagents. A versatile approach to enantioenriched alcohols
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(matrix presented) Chiral α-(carbamoyloxy)alkyllithium reagents, prepared using Hoppe's sBuLi/(-)-sparteine methodology, were transmetalated with ZnCl2. Further transmetalation with CuCN with overall retention of configuration gave chiral species that reacted with various electrophiles to give enantiomerically pure alcohols after deprotection. A short, highly efficient synthesis of an industrially relevant pheromone, japonilure, illustrates the value of the methodology.
- Papillon, Julien P. N.,Taylor, Richard J. K.
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p. 119 - 122
(2007/10/03)
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- Asymmetric synthesis of the Japanese beetle pheromone via boronic esters
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The pheromone of the Japanese beetle, [R-(Z)]-5-(1-decenyl)dihydro-2(3H)-furanone (7), has been synthesized efficiently in high enantiomeric purity via 1,2-dicyclohexyl-1,2-ethanediol boronic esters. The synthetic route involves reaction of an α-chloro boronic ester with an alkynyllithium, and provides the first successful example of this substitution process in an asymmetric synthesis.
- Hiscox, William C.,Matteson, Donald S.
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p. 314 - 317
(2007/10/03)
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- The synthesis of three important lactones via an enzymatic resolution strategy that improves ee's and yields
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Three important lactones have been synthesized in high enantiomeric purity by a complimentary, two-enantioselective-step strategy. In this approach, an enzymatic kinetic resolution is performed on a starting material that has been enriched in the faster-reacting enantiomer by an earlier enantioselective step. The results show that percent conversions, yields and ee's can be dramatically increased by this complimentary approach, and they illustrate how modestly enantioselective techniques can be combined with kinetic resolution procedures to yield optically pure compounds. The utility of many modestly enantioselective (and hence sometimes disregarded) techniques can be enhanced thereby.
- Taylor,Atkinson,Almli,Carr,Van Huis,Whittaker
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p. 157 - 164
(2007/10/02)
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- Chiral Synthesis of (R)-(-)-(5Z)-4-Hydroxy-5-tetradecenoic Acid-4-lactone
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(R)-(-)-(5Z)-4-Hydroxy-5-tetradecenoic acid-4-lactone has been synthesized from D-glucose as the precursor.Regio and stereoselective transformations of hydroxyl groups as well as protection-deprotection protocols provide a novel route to this compound. - Keywords: Chiral Pool, Lactone, Isopropylidene, Olefination, Pheromone
- Salas-Reyes, V.
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p. 1537 - 1542
(2007/10/03)
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- Method for manufacturing 4-substituted-Y-lactone and novel substance
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An alkynyl group having a triple bond at the carbon atom at the 1-position is introduced to a carbon atom at the 1-position of 2,3-O-isopropylidene-D-ribofuranose. The diol part is then cleaved to obtain a lactol compound. This lactol compound is oxidized to obtain a lactone compound. The ketal part of the lactone compound is hydrolyzed and the compound is further subjected to a reduction reaction. The hydroxyl groups at the 2- and 3-positions are then eliminated, and the double bond between the 2- and 3-positions of the resultant compound is reduced to obtain a 4-substituted-γ-lactone.
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- Synthesis of sex pheromones of the Japanese Beetle and Cupreus Chafer Beetle
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The pheromones (1a,1b) of two insect pests, the Japanese Beetle (Popillia japonica, Newman) and Cupreus Chafer Beetle (Anomala cuprea, Hope), were synthesized. Starting from protected D-Ribose, 1a was prepared in 8 steps with a 30% total yield. The same chemistry was demonstrated for the synthesis of 1b.
- Koseki, Koshi,Ebata, Takashi,Kadokura, Teruyuki,Kawakami, Hiroshi,Ono, Mikio,Matsushita, Hajime
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p. 5961 - 5968
(2007/10/02)
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- A NOVEL APPROACH TO CHIRAL CYCLOBUTANES- -AN ENANTIOSELECTIVE TOTAL SYNTHESIS OF (+)-(S,Z)-5-(1-DECENYL)DIHYDRO-2(3H)-FURANONE AND (-)-(R,Z)-5-(1-DECENYL)DIHYDRO-2(3H)-FURANONE
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An enantioselective synthesis of (+)-(S,Z)-5-(1-decenyl)-dihydro-2(3H)-furanone (25) and (-)-(R,Z)-5-(1-decenyl)dihydro-2(3H)-furanone (26) was achieved starting with either (10) or (11) prepared by reduction of the chiral cyclobutanone (8) which was derived stereospecifically from the cyclopropyl carbinol (6) by ring expansion reaction.
- Nemoto, Hideo,Ishibashi, Hiroki,Mori, Masahiko,Fujita, Shigekazu,Fukumoto, Keiichiro
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p. 1237 - 1240
(2007/10/02)
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- Ring Expansion of Cyclopropylmethanols to Cyclobutanes - An Enantioselective Total Synthesis of (R)-(+)-Dodecan-5-olide, and (S)-(+)- and (R)-(-)-5-dihydrofuran-2(3H)-one
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A novel and convenient route to chiral cyclobutanones (8) and (9) by ring expansion of the cyclopropylmethanols (6) and (7) was developed, leading to an enantioselective total synthesis of (R)-(+)-dodecan-5-olide (25), and (S)-(+)- and (R)-(-)-5-dihydrofuran-2(3H)-one (35) and (36) (the pheromone of the Japanese beetle).
- Nemoto, Hideo,Ishibashi, Hiroki,Mori, Masahiko,Fujita, Shigekazu,Fukumoto, Keiichiro
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p. 2835 - 2840
(2007/10/02)
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- A Convenient Synthesis of (R)-Japonilure
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The title pheromone has been synthesised in high optical purity using easily accessible (S)-glycerol-2,3-acetonide (2) as the starting chiron.
- Chattopadhyay, S.,Mamdapur, V. R.,Chadha, M. S.
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p. 1299 - 1303
(2007/10/02)
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- Syntheses of Chiral γ-Lactones from D- and L-Arabinoses
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Convenient synthetic routes to 4R- and 4S-γ-lactones from respective D- and L-arabinoses are developed.An application of the routes to the chiral synthesis of a sex pheromone of Japanese beetle is presented.
- Nishida, Yoshihiro,Konno, Masao,Hori, Hiroshi,Ohrui, Hiroshi,Meguro, Hiroshi
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p. 635 - 640
(2007/10/02)
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- Synthetic Applications of the Enantioselective Reduction by Binaphthol-Modified Lithium Aluminum Hydride Reagents
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The reduction of prochiral carbonyl substrates with the chiral binaphthol-modified lithium aluminum hydride reagents provides an effective means for preparing alcoholic products of high optical purity.The reaction is applicable to a variety of structurally diverse unsaturated carbonyl compounds such as aromatic ketones, acetylenic ketones, olefinic ketones and aldehydes, etc.Either of the antipodes is obtainable in a predictable manner by choosing the handedness of the auxiliary binaphthol ligand.The utility is exemplified by the efficiently stereocontrolled synthesis of prostaglandin intermediates, some insect pheromones, chiral primary terpenic alcohols, optically active styrene oxide, etc.
- Noyori, R.,Tomino, I.,Yamada, M.,Nishizawa, M.
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p. 6717 - 6725
(2007/10/02)
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- Asymmetric Synthesis of (R,Z)-(-)-5-(1-Decenyl)oxacyclopentan-2-one, the Pheromone of the Japanese Beetle
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Optically pure (R,Z)-(-)-5-(1-decenyl)oxacyclopentan-2-one, the pheromone of Popillia japonica, was synthesized by employing the asymmetric reduction of an acetylenic keto ester as the key-step.
- Senda, Shuji,Mori, Kenji
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p. 2595 - 2598
(2007/10/02)
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- Synthesis of Optically Pure (R,Z)-5-Dec-1-enyloxacyclopentan-2-one, the Sex Pheromone of the Japanese Beetle
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Optically pure (R,Z)-5-dec-1-enyloxacyclopentan-2-one (1) has been synthesised from methyl 4-oxotetradec-5-ynoate (2) by chiral reduction with 9-(pinan-3-yl)-9-borabicyclononane (3) which yielded the R-alcohol (4), in 74percent enantiomeric excess.This was further purified by recrystallisation of the salt formed from the phthalate ester of compound (4) and (+)-α-methylbenzylamine and then hydrolysed and converted into (R,Z)-(-)-(1).
- Baker, Raymond,Rao, V. Bhaskar
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