Synthesis of C15–C27 segment of venturicidine X by utilizing desymmetrization protocol

Yadav, J. S.; Hossain, Sk. Samad; Mohapatra, Debendra K.

doi:10.1016/j.tetlet.2010.05.148

Cited by 8 publications

(3 citation statements)

References 25 publications

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“…In 2010, Yadav et al. achieved the synthesis of C15−C27 fragment of venturicidine X using desymmetrization protocol, substrate‐controlled Grignard reaction, Barton‐McCombie reaction, Wittig reaction, Sharpless epoxidation, and TBSOTf‐mediated rearrangement to produce an aldol product through a non‐aldol route as the key steps with 6.4 % overall yield [21] . The exo‐alkylated lactone 8 was subjected for acid‐catalyzed methanolysis, LiAlH 4 ‐mediated reduction, and IBX oxidation to afford the aldehyde 139 .…”

Section: Introductionmentioning

confidence: 99%

Desymmetrisation of meso‐2,4‐Dimethyl‐8‐oxabicyclo[3.2.1]‐oct‐6‐ene‐3‐ol and its Application in Natural Product Syntheses

Tadiparthi

Anand

Sakirolla

et al. 2021

The Chemical Record

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The compounds containing chiral centers and different functional groups serve as magnificent building blocks for the preparation of various natural products that are having immense biological activity. “Dimethyl‐8‐oxa‐bicyclo[3.2.1]oct‐6‐en‐3‐ol” is one of the wonderful synthons to construct multiple stereo centers at a time during the asymmetric synthesis. In this account, we discuss our research efforts toward the synthesis of various simple and complex natural products from the past three decades (1995–2020) by using dimethyl‐8‐oxa‐bicyclo[3.2.1]oct‐6‐en‐3‐ol as a synthon. Moreover, the synthetic utility of this starting material was investigated and well demonstrated. Further, we executed the desymmetrization of dimethyl‐8‐oxa‐bicyclo[3.2.1]oct‐6‐en‐3‐ol by hydroboration to get different chiral centers. After obtaining the stereocenters, we could manage either the fragment, formal or total synthesis of natural products, by simple protection and deprotection sequence followed by C−C bond formation steps.

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Section: Introductionmentioning

confidence: 99%

Desymmetrisation of meso‐2,4‐Dimethyl‐8‐oxabicyclo[3.2.1]‐oct‐6‐ene‐3‐ol and its Application in Natural Product Syntheses

Tadiparthi

Anand

Sakirolla

et al. 2021

The Chemical Record

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“…In continuation of our program on the total synthesis of polyketide natural products, we identified the symmetric precursor 12 for a desymmetrization strategy and have utilized it for the synthesis of several natural products . Accordingly, compound 12 has been subjected to chiral hydroboration to yield 13 which was converted to known acetal 11 . 11 on reduction with LiAlH 4 provided alcohol 14 in 93% yield (Scheme ).…”

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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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“…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 temperature.…”

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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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Synthesis of C15–C27 segment of venturicidine X by utilizing desymmetrization protocol

Cited by 8 publications

References 25 publications

Desymmetrisation of meso‐2,4‐Dimethyl‐8‐oxabicyclo[3.2.1]‐oct‐6‐ene‐3‐ol and its Application in Natural Product Syntheses

Desymmetrisation of meso‐2,4‐Dimethyl‐8‐oxabicyclo[3.2.1]‐oct‐6‐ene‐3‐ol and its Application in Natural Product Syntheses

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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