Total Synthesis of Asimicin and Bullatacin

Avedissian, Hovsep; Sinha, Santosh C.; Yazbak, Ahmad; Sinha, Anjana; Neogi, Partha; Sinha, Subhash C.; Keinan, Ehud

doi:10.1021/jo000500a

Cited by 79 publications

(39 citation statements)

References 58 publications

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“…32 When 83 was subjected to the conditions of the Jones oxidation, the tetrahydropyran (THP) protecting group was removed, and the resulting alcohol underwent direct oxidation to the carboxylic acid 84 in 82% yield. Initial attempts to partially reduce the alkyne moiety of 84 with Lindlar’s catalyst gave inseparable mixtures of cis- and trans- isomers of 81 (~10:1 cis:trans ).…”

Section: Resultsmentioning

confidence: 99%

Enantioselective Halolactonization Reactions using BINOL-Derived Bifunctional Catalysts: Methodology, Diversification, and Applications

et al. 2018

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A general protocol is described for inducing enantioselective halolactonizations of unsaturated carboxylic acids using novel bifunctional organic catalysts derived from a chiral binaphthalene scaffold. Bromo- and iodolactonization reactions of diversely substituted, unsaturated carboxylic acids proceed with high degrees of enantioselectivity, regioselectivity, and diastereoselectivity. Notably, these BINOL-derived catalysts are the first to induce the bromo- and iodolactonizations of 5-alkyl-4(Z)-olefinic acids via 5-exo mode cyclizations to give lactones in which new carbon–halogen bonds are created at a stereogenic center with high diastereo- and enantioselectivities. Iodolactonizations of 6-substituted-5(Z)-olefinic acids also occur via 6-exo cyclizations to provide δ-lactones with excellent enantioselectivities. Several notable applications of this halolactonization methodology were developed for desymmetrization, kinetic resolution, and epoxidation of Z-alkenes. The utility of these reactions is demonstrated by their application to a synthesis of precursors of the F-ring subunit of kibdelone C and to the shortest catalytic, enantioselective synthesis of (+)-disparlure reported to date.

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Section: Resultsmentioning

confidence: 99%

Enantioselective Halolactonization Reactions using BINOL-Derived Bifunctional Catalysts: Methodology, Diversification, and Applications

et al. 2018

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“…Similar rhenium-mediated type C oxidative cyclizations were also successfully applied in total syntheses of further acetogenins by Sinha and Keinan, e.g., asimicin [112–113], bullatacin [112–114], trilobacin [115] and even to the tris-THF acetogenins goniocin [116] and cyclogoniodenin T [116]. …”

Section: Reviewmentioning

confidence: 99%

The direct oxidative diene cyclization and related reactions in natural product synthesis

Adrian¹,

Gross²,

Stark³

2016

Beilstein J. Org. Chem.

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SummaryThe direct oxidative cyclization of 1,5-dienes is a valuable synthetic method for the (dia)stereoselective preparation of substituted tetrahydrofurans. Closely related reactions start from 5,6-dihydroxy or 5-hydroxyalkenes to generate similar products in a mechanistically analogous manner. After a brief overview on the history of this group of transformations and a survey on mechanistic and stereochemical aspects, this review article provides a summary on applications in natural product synthesis. Moreover, current limitations and future directions in this area of chemistry are discussed.

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“…In 2000, the group of Sinha and Keinan reported the total synthesis of asimicin ( 260 ) [ 97 ] and demonstrated the advantages of three different strategies for the synthesis of the tricyclic intermediate 274 ( Scheme 37 ), which represented the key fragment of the bis-THF ACGs. The naked carbon skeleton strategy was based on the production of all asymmetric centers by selective placement of the oxygen functions onto an unsaturated, non-functionalized carbon skeleton 271 .…”

Section: Reviewmentioning

confidence: 99%

“…In 2000, the group of Sinha and Keinan reported the total synthesis of bullatacin ( 311 ) [ 97 ] and demonstrated the advantages of three different strategies for the synthesis of the tricyclic intermediates 274 using the same procedure as in the total synthesis of asimicin ( Scheme 42 ).…”

Section: Reviewmentioning

confidence: 99%

Recent progress on the total synthesis of acetogenins from Annonaceae

Li¹,

Shi²,

Tang³

et al. 2008

Beilstein J. Org. Chem.

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An overview of recent progress on the total synthesis of acetogenins from Annonaceae during the past 12 years is provided. These include mono-tetrahydrofurans, adjacent bis-tetrahydrofurans, nonadjacent bis-tetrahydrofurans, tri-tetrahydrofurans, adjacent tetrahydrofuran-tetrahydropyrans, nonadjacent tetrahydrofuran-tetrahydropyrans, mono-tetrahydropyrans, and acetogenins containing only γ-lactone. This review emphasizes only the first total synthesis of molecules of contemporary interest and syntheses that have helped to correct structures. In addition, some significant results on the novel synthesis and structure-activity relationship studies of annonaceous acetogenins are also introduced.

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Total Synthesis of Asimicin and Bullatacin

Cited by 79 publications

References 58 publications

Enantioselective Halolactonization Reactions using BINOL-Derived Bifunctional Catalysts: Methodology, Diversification, and Applications

Enantioselective Halolactonization Reactions using BINOL-Derived Bifunctional Catalysts: Methodology, Diversification, and Applications

The direct oxidative diene cyclization and related reactions in natural product synthesis

Recent progress on the total synthesis of acetogenins from Annonaceae

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