Enantioselective Total Synthesis of (+)‐Vittatalactone

Yadav, J. S.; Yadav, Nagendra Nath; Rao, T. Siva; Reddy, B. V. Subba; Ghamdi, Ahmad Al Khazim Al

doi:10.1002/ejoc.201100354

Cited by 29 publications

(8 citation statements)

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“…The 13 C NMR spectrum, which showed 16 carbon signals without overlapping, is an important datum for conrming the diastereomeric purity of its enantioselective synthesis. [272][273][274] Females of a scarab beetle species produce cuticular hydrocarbons with unprecedented hexamethyl and pentamethyl structures (14 and 15). Their mass spectra exhibited molecular ions at m/z 394 and 380, respectively, and the formulas C 28 H 58 and C 27 H 56 were conrmed by accurate mass measurements.…”

Section: Determination Of the Branch Positions Of Tetra- Penta- And H...mentioning

confidence: 99%

“…Evans chiral auxiliaries were also utilized in the syntheses of tri-and pentamethyl pheromones (49, 90, and 91) to induce asymmetry at one of the methyl-branched stereogenic centers. 158,266,274 (2) Synthesis via the reaction of an epoxy compound. Several interesting pheromone syntheses via chiral epoxy intermediates have been published.…”

Section: Application Of Stereoselective Reactionsmentioning

confidence: 99%

“…Since the chiral monoacete is a useful synthon for synthesizing skipped polymethyl-branched compounds with a syn conguration, it has been employed for the total synthesis of 49 and vittatalactone (91) (Route 4). 158,274 Aer chain elongation by means of a Wittig reaction, the resulting carboxylic acid was coupled with an Evans chiral oxazolinone using pivaloyl chloride in the presence of Et 3 N and LiCl. Enantioselective methylation of the enolate with MeI (R-1-4b) furnished a compound with a 1,3,5-trimethyl structure, which was further modied to the chain moieties of (2R,4R,6R,8R)-49 and (2R,3R,4S,6S,8S)-91.…”

Section: Syntheses Of 13-dimethyl and More Branched Pheromonesmentioning

confidence: 99%

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Chiral methyl-branched pheromones

Ando

Yamakawa

2015

Nat. Prod. Rep.

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Insect pheromones are some of the most interesting natural products because they are utilized for interspecific communication between various insects, such as beetles, moths, ants, and cockroaches. A large number of compounds of many kinds have been identified as pheromone components, reflecting the diversity of insect species. While this review deals only with chiral methyl-branched pheromones, the chemical structures of more than one hundred non-terpene compounds have been determined by applying excellent analytical techniques. Furthermore, their stereoselective syntheses have been achieved by employing trustworthy chiral sources and ingenious enantioselective reactions. The information has been reviewed here not only to make them available for new research but also to understand the characteristic chemical structures of the chiral pheromones. Since biosynthetic studies are still limited, it might be meaningful to examine whether the structures, particularly the positions and configurations of the branched methyl groups, are correlated with the taxonomy of the pheromone producers and also with the function of the pheromones in communication systems.

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Section: Determination Of the Branch Positions Of Tetra- Penta- And H...mentioning

confidence: 99%

Section: Application Of Stereoselective Reactionsmentioning

confidence: 99%

Section: Syntheses Of 13-dimethyl and More Branched Pheromonesmentioning

confidence: 99%

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Chiral methyl-branched pheromones

Ando

Yamakawa

2015

Nat. Prod. Rep.

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“…Our approach for the synthesis of aldehyde 7 (segment B C13–C17) is delineated in Scheme . Accordingly, the synthesis began with the known diacid which on reduction with LiAlH 4 provides precursor meso diol 33 that was subjected to desymmetrization by using porcine pancreatic lipase (PPL) and vinyl acetate in THF at ambient conditions furnishing the monoacetate 34 in 47% yield with ≥95% ee along with the meso -diacetate . Alcohol 34 was converted into corresponding benzyl ether 35 and subjected to reduction with LiAlH 4 to yield alcohol 36 .…”

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confidence: 99%

Formation of Substituted Tetrahydropyrans through Oxetane Ring Opening: Application to the Synthesis of C1–C17 Fragment of Salinomycin

2014

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“…6 Our group previously accomplished the total synthesis of (+)-vittatalactone by using an enzymatic desymmetrization approach. 7 We herein report the total synthesis of both enantiomers of vittatalactone, (+)-1a and (-)-1b, by exploiting our previously developed desymmetrization strategy.…”

mentioning

confidence: 99%

Enantioselective Total Synthesis of (+)- and (-)-Vittatalactone

Yadav¹,

Srinivas²,

Kumar³

et al. 2012

Synthesis

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The asymmetric total synthesis of both enantiomers of (+)-and (-)-vittatalactone has been achieved using a desymmetrization strategy to create three methyl chiral centers. The key steps in these total syntheses are Myers asymmetric alkylation, coppercatalyzed alkylation, 2,2,6,6-tetramethyl-1-piperidinyloxyl-(diacetoxyiodo)benzene [TEMPO-PhI(OAc 2 )] promoted oxidation and p-toluenesulfonyl chloride mediated lactonization. The products are obtained in good overall yields employing linear synthetic sequences.Polydeoxypropionates are an important class of biologically active molecules and the development of methods for their synthesis has led to the discovery of new strategies. The use and application of pheromones is expected to grow more rapidly and widely in the coming years because of increasing concerns of consumers about residual chemicals from agricultural products. The chemical syntheses of such compounds will ensure ample supplies and facilitate their practical use in agriculture and forestry. Vittatalactone, a structurally unique pheromone, was isolated from the striped cucumber beetle, Acalymma vittatum by Francke 1 and coworkers in 2005. It contains a novel trans-configured b-lactone moiety and an all synconfigured tetramethyl substituted alkyl chain as structural features. Breit et al. 2 have assigned the relative and absolute configurations of natural (+)-1a and unnatural (-)-1b 3 vittatalactones through total synthesis. Figure 1 Structures of (+)-and (-)-vittatalactoneIn continuation of our research on synthetic pheromones, 4,5 and our ongoing studies on the synthesis of biologically active molecules by exploiting desymmetrization strategies, the interesting structural features and biological activity of vittatalactone have attracted our attention toward its synthesis. Two total syntheses of vittatalactone have been reported: as key steps, the method of Breit and coworkers involved an o-diphenylphosphinobenzoic acid (o-DPPB) directed allylic substitution, 2 whilst that of Schneider et al. utilized an iridium-catalyzed hydrogenation. 6 Our group previously accomplished the total synthesis of (+)-vittatalactone by using an enzymatic desymmetrization approach. 7 We herein report the total synthesis of both enantiomers of vittatalactone, (+)-1a and (-)-1b, by exploiting our previously developed desymmetrization strategy.Our retrosynthetic strategy is shown in Scheme 1 in which both enantiomers could be easily obtained from the common intermediate 5 by utilizing the appropriate chiral boron reagent.The synthesis of (+)-vittatalactone started from the known triol 3a 8 which was readily obtained from 5 using a desymmetrization approach. Protection of the 1,3-diol moiety was accomplished using 2,2-dimethoxypropane [Me 2 C(OMe) 2 ] 9 and a catalytic amount of p-toluenesulfonic acid in dichloromethane at 0 °C to afford 6a in 85% yield. The primary hydroxy group in 6a was converted into the corresponding iodide to give 7a 10 in 94% yield using triphenylphosphine, imidazole and iodine in toluene at room tempera...

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Enantioselective Total Synthesis of (+)‐Vittatalactone

Abstract: An enantioselective asymmetric total synthesis of (+)-vittatalactone has been accomplished employing enzymatic desymmetrization approach to create two methyl chiral centres. Other key steps involved are Wittig reaction, Evan's asym-

Cited by 29 publications

References 32 publications

Chiral methyl-branched pheromones

Chiral methyl-branched pheromones

Formation of Substituted Tetrahydropyrans through Oxetane Ring Opening: Application to the Synthesis of C1–C17 Fragment of Salinomycin

Enantioselective Total Synthesis of (+)- and (-)-Vittatalactone

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