Saline hydrides and superbases in organic reactions. IX. Acetylene zipper. Exceptionally facile contrathermodynamic multipositional isomeriazation of alkynes with potassium 3-aminopropylamide

Brown, Charles A.; Yamashita, Ayako

doi:10.1021/ja00837a034

Cited by 219 publications

(75 citation statements)

References 1 publication

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“…[24] By using 1 mol-% of (R)-[{RuCl(tol-BINAP)} 2 (μ-Cl) 3 The installation of the long spacer of mycoside B was preceded by a four-step synthesis of building block 20, as depicted in Scheme 3. Despite the potential of the alkyne zipper reaction to afford α,ω-bifunctionalized aliphatic chains of different lengths, its application to natural product synthesis has been very infrequent since its introduction by Brown and Yamashita in 1975. [25,26] Here we used the reaction to shift the triple bond in commercially available alkyne 7 to the terminal position (compound 17).…”

Section: Resultsmentioning

confidence: 99%

Total Synthesis of the Phenolic Glycolipid Mycoside B and the Glycosylated p‐Hydroxybenzoic Acid Methyl Ester HBAD‐I, Virulence Markers of Mycobacterium tuberculosis

Barroso¹,

Geerdink²,

Horst³

et al. 2013

Eur J Org Chem

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The phenolic glycolipid mycoside B, present in Mycobacterium bovis and hypervirulent strains of Mycobacterium tuberculosis, has been synthesized for the first time. Multiple methyl groups were introduced by the extensive use of catalytic asymmetric 1,4‐addition reactions, asymmetric hydrogenation of a β‐keto ester afforded the basis for the central 1,3‐diol moiety, and introduction of the 2‐O‐methyl‐α‐L‐rhamnoside unit was achieved by stereoselective glycosylation with p‐iodophenol and subsequent Sonogashira coupling, providing a basis for the generation of analogues. In addition, the related monosaccharide HBAD‐I, present in the same species, has been efficiently synthesized for the first time by selective methylation of the hydroxy group at C‐2 of a rhamnoside.

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Section: Resultsmentioning

confidence: 99%

Total Synthesis of the Phenolic Glycolipid Mycoside B and the Glycosylated p‐Hydroxybenzoic Acid Methyl Ester HBAD‐I, Virulence Markers of Mycobacterium tuberculosis

Barroso¹,

Geerdink²,

Horst³

et al. 2013

Eur J Org Chem

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“…Dec-9-yn-1-ol was prepared from commercially available dec-2-yn-1-ol by the acetylene Zipper reaction [10] and the aryl iodide (2) was prepared by a literature method [11]. Various palladium catalysed coupling reactions of iodide (2) with dec-9-yn-1-ol were tried to optimise the yield of alkyne (3) using different bases, co-catalysts, solvents and temperatures [12 -18].…”

Section: Resultsmentioning

confidence: 99%

A High-Yielding Synthesis of the Naturally Occurring Antitumour Agent Irisquinone

2000

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“…The extremely fast reaction rates observed with the original isomerization reagents were attributed to a concerted, bimolecular mechanism in;olving the bidentate nature of the base (2). A cycle was postulated wherein the amide nitrogen would abstract a proton from the carbon next to the triple bond and the resultant allenic anion would abstract a proton from the other nitrogen of the base.…”

Section: Resultsmentioning

confidence: 99%

Some alkali metal alkyl amides as alkyne isomerization reagents: selective isomerization of one triple bond of a diynol

Abrams¹,

Nucciarone²,

Steck³

1983

Can. J. Chem.

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61, 1073 (1983).The lithium and sodium salts of 1.2-diaminocthanc. l,3-diarninopropane. n-butylamine, and the lithium salt of isobutylaminc were studied as potential rcapcnts for isomcrization of triple bonds in alkyn-I-01s. The sodium salts of the diamincs afforded high yields of the o-alkyn-1-01. Somewhat surprisingly. the sodium salt of n-butylamine also effects isomerization to the terminal position. The lithium salt of 1,3-diaminopropanc gave the highest conversion of 2-to 3-alkyn-1-01, A novel, selective rearrangement of one triple bond of a diynol. a 2.0-to 3.w-diyn-1-01 isomcrization, was incorporated into a synthesis of the insect sex pheromone 3.13-octadccadienol acetate. On a 6valuC I'utilisd des sels de sodium et dc lithium du diarnino-1.2 Cthane. du diamino-1.3 propane, de la n-butylaminc et du sel de lithium dc I'isobutylamine en tant qu'apents potentiels d'isomdrisation des triples liaisons des alcynols-I. Les scls dc sodium des dialnines donnent des rendemcnts dlevds en o-alcynols-I. Par opposition le sel de sodium de la n-butylamine affcctc aussi I'isornCrisarion vers la position terminale. LC sel dc lithium du diamino-1.3 propane donne le plus fort pourcentage dc transformation des alcync-l 01s-I en alcyne-3 01s-I. Dans le cadre dc la synthkse de la phCromone scxuclle des insectes, I 'acetate d'octadecadienc-3.13 ol, on a introduit une nouvelle transposition sdlcctive d'une triple liaison d'un diynol ii savoir I'isomdrisation d'un 2.0-diync 01-1 en un 3,o-diyne ol-I.[Traduit par le journal]

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Saline hydrides and superbases in organic reactions. IX. Acetylene zipper. Exceptionally facile contrathermodynamic multipositional isomeriazation of alkynes with potassium 3-aminopropylamide

Cited by 219 publications

References 1 publication

Total Synthesis of the Phenolic Glycolipid Mycoside B and the Glycosylated p‐Hydroxybenzoic Acid Methyl Ester HBAD‐I, Virulence Markers of Mycobacterium tuberculosis

Total Synthesis of the Phenolic Glycolipid Mycoside B and the Glycosylated p‐Hydroxybenzoic Acid Methyl Ester HBAD‐I, Virulence Markers of Mycobacterium tuberculosis

A High-Yielding Synthesis of the Naturally Occurring Antitumour Agent Irisquinone

Some alkali metal alkyl amides as alkyne isomerization reagents: selective isomerization of one triple bond of a diynol

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