Asymmetric epoxidation provides shortest routes to four chiral epoxy alcohols which are key intermediates in syntheses of methymycin, erythromycin, leukotriene C-1, and disparlure

Rossiter, Bryant E.; Katsuki, Tsutomu; Sharpless, K. Barry

doi:10.1021/ja00392a038

Cited by 330 publications

(66 citation statements)

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“…The predominant approach for the asymmetric epoxidation of allylic alcohols is through the titanium-catalyzed Sharpless epoxidation, which can usually achieve the enantioselective epoxidation of primary allylic alcohols catalyzed by l-(+)/d-(−)-diisopropyl tartrate and titanium tetraisopropoxide (Ti(O-i-Pr) 4 ) using tert-butyl hydroperoxide (TBHP) as the oxidant [10,22,69,70]. The absolute configuration of the resulting epoxide can be easily predicted using a rule developed by Sharpless, which correlates to the enantiomer of the tartrate used.…”

Section: Classic Methods For the Asymmetric Epoxidation Of Allylic Almentioning

confidence: 99%

Biocatalysis as an alternative for the production of chiral epoxides: A comparative review

Lin

Liu

Wang

et al. 2011

Journal of Molecular Catalysis B: Enzymatic

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Section: Classic Methods For the Asymmetric Epoxidation Of Allylic Almentioning

confidence: 99%

Biocatalysis as an alternative for the production of chiral epoxides: A comparative review

Lin

Liu

Wang

et al. 2011

Journal of Molecular Catalysis B: Enzymatic

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“…[22] Ring opening of the resulting epoxy alcohol 2 with application of excess AlMe 3 at low temperature provided (+)-methyl (5R,6R)-6,7-dihydroxy-5-methylheptanoate (3, Ͼ95 % ee), establishing the single stereogenic center of the natural product. Cleavage of the resulting diol with periodate yielded an aldehyde that, when subjected to the Seyferth-Gilberts reagent, produced the terminal alkyne 4 required for a subsequent palladium coupling reaction.…”

Section: Danishefsky's Synthesis -Evidence That (+)-Frondosin B Occurmentioning

confidence: 99%

The Frondosins: An Unusual Synthetic and Stereochemical Journey

VanHeyst

Wright

2014

Eur J Org Chem

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Isolated from the marine sponge Dysidea frondosa, the frondosin family of meroterpenoid natural products were shown to be antagonists of the binding of the cytokine interleukin‐8 to its receptor. With implications of interleukin‐8 management being associated with a wide range of acute and chronic inflammatory disorders, as well as tumor progression and/or metathesis, there have been a multitude of syntheses of these natural products in the hopes of developinging new pharmacological agents. However, assignment of the absolute configurations of these natural products became unclear, because the first two syntheses of frondosin B, by Danishefsky and by Trauner, produced conflicting assignments for the single stereogenic center at C8. Here we describe the initial stereochemical mystery surrounding the Danishefsky and Trauner syntheses and provide evidence through ensuing syntheses of frondosins B and A that resolve this issue. These subsequent asymmetric syntheses have established that (1) the natural product occurs as the R enantiomer, and (2) a late‐stage stereochemical inversion occurred during the Trauner and Wright syntheses of frondosin B.

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“…nH,O/NaIO,, Sharpless and coworkers had re-HELVETICA CHIMICA ACTA ~ Vol. 71 (1988) ported that functional groups such as epoxides and other cyclic ethers were compatible with the reaction conditions [I31 [14]. While CCl,/H,O was the standard solvent system for RuO, oxidations, it was found that acetonitrile serves to greatly accelerate the rate of reaction [ 131.…”

Section: XII 87)mentioning

confidence: 99%

Note on the Preparation of 1,2‐Diketones from Acetylenes

Zibuck

Seebàch²

1988

Helvetica Chimica Acta

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A mild method for the oxidation of acetylenes to 1,2-diketones using NaI04/RuOz is described. An investigation on the compatibility of various functional groups with this oxidizing agent is reported.In connection with our recent work on the total synthesis of gloeosporone') (Scheme I ) [l] [2], we required an efficient method for the oxidation of an acetylene to the corresponding 1,Zdiketone in the presence of an ester and a protected alcohol group. A S h e m e I , , , , OTBS -HllC5 TBS= (t-Bu)Me,Si search of the literature revealed many reagents for this transformation; however, the substrates in all cases were simple aliphatic or aromatic acetylenes. The known methods are summarized in Scheme 2.Of these reagents, Ru(VII1) appeared to be suitable for our purpose, especially since in the cleavage of olefins with RuCI, . nH,O/NaIO,, Sharpless and coworkers had re-

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Asymmetric epoxidation provides shortest routes to four chiral epoxy alcohols which are key intermediates in syntheses of methymycin, erythromycin, leukotriene C-1, and disparlure

Cited by 330 publications

References 0 publications

Biocatalysis as an alternative for the production of chiral epoxides: A comparative review

Biocatalysis as an alternative for the production of chiral epoxides: A comparative review

The Frondosins: An Unusual Synthetic and Stereochemical Journey

Note on the Preparation of 1,2‐Diketones from Acetylenes

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