Oxidative Degradation of γ-Butyrolactons into 1,3-Diols via a Criegee Rearrangement of Peroxosulfonates. An Enantioselective Synthesis of Compactin Lactone and its Diastereomer

Menges, Markus; Brückner, Reinhard

doi:10.1055/s-1993-22645

Cited by 26 publications

(2 citation statements)

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“…Secondly, proceeding in accordance with Scheme implemented the synthetic equivalence between a γ‐lactone and a (protected) 1,3‐diol. This was a topic, which we were studying at the time …”

Section: The Sharpless Asymmetric Dihydroxylation Of βγ‐Unsaturatmentioning

confidence: 99%

Nonracemic γ‐Lactones from the Sharpless Asymmetric Dihydroxylation of β,γ‐Unsaturated Carboxylic Esters

Neumeyer

Brückner

2016

Eur J Org Chem

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Since Sharpless' discovery of the asymmetric dihydroxylation of C=C double bonds in the late 1980s this reaction has become a powerful tool of synthetic organic chemistry. As a consequence, this transformation has been reviewed repeatedly and extensively. The present microreview focuses on Sharpless' asymmetric dihydroxylations (from here on “SADs”) of β,γ‐unsaturated carboxylic esters. These SADs differ from most others in that they provide not nonracemic 1,2‐diols but follow‐up products thereof. Bearing ester groups at appropriate distances, the SAD‐based 1,2‐diols obtained from β,γ‐unsaturated carboxylic esters lactonize readily under SAD conditions. Accordingly, SADs of β,γ‐unsaturated carboxylic esters furnish nonracemic β‐hydroxy‐γ‐lactones in a single operation. We show that this SAD route represents a – or even the most – potent easy‐to‐handle route to nonracemic butanolides and butenolides “of almost all kinds”. The span covered is from pioneering racemic work to applications in natural product synthesis. Some non‐butanolide and non‐butenolide target syntheses are included, especially those of tetrahydrofurans.

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Section: The Sharpless Asymmetric Dihydroxylation Of βγ‐Unsaturatmentioning

confidence: 99%

Nonracemic γ‐Lactones from the Sharpless Asymmetric Dihydroxylation of β,γ‐Unsaturated Carboxylic Esters

Neumeyer

Brückner

2016

Eur J Org Chem

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“…This gave an 8:92 ratio of endo : exo diastereomers ( 3a : 3b ) that were easily separable by chromatography. Endo diasteromer 3a was obtained by equilibration of the mixture using LDA followed by quenching with saturated sodium sulfate . This led to a 1:1 mixture of 3a : 3b from which the endo diastereomer 3a was easily isolated in 40% yield.…”

Section: Introductionmentioning

confidence: 99%

Scope and Limitations in Palladium-Catalyzed Substitution Reactions of Unsaturated Fused Lactones

et al. 1997

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The palladium-catalyzed nucleophilic substitution of C-4-substituted 2-oxabicyclo[3.3.0]oct-7-en-3-ones (unsaturated, fused lactones) have been studied particularly in relation to how electronic and steric factors influenced the rate and efficiency of substitution reactions. Thus, a range of R-substituted lactones were prepared (X ) H, Me, OH, OAc, Br, N 3 , NHCBZ) and subjected to palladium-catalyzed substitution reaction with diethyl sodiomalonate, and it was found that reaction rates increased with increasing electron-withdrawing ability of the substituent and that there was a strong correlation between rate and pK a of the corresponding substituted acetic acids (XCH 2 -CO 2 H). The only exception to the correlation was with X ) OH, in which case the endo isomer reacted considerably faster than expected and the exo isomer reacted much slower than expected. It was also found that the rates of reaction of the endo isomers were greater than the exo isomers. The increased rates have been accounted for by a shift in equilibrium between the lactone and the π-allyl palladium intermediate toward the latter species due to the increased stability of the carboxylate (electronic effects) or relief of steric hindrance in the starting lactone. The scope and limitations of the palladium-catalyzed substitution reaction were studied by reacting a range of lactones with a range of nucleophiles. Lactones with unactivated leaving groups such as 2 (X ) H) coupled efficiently with good nucleophiles such as malonate but only poorly with less reactive nucleophiles such as azide. Lactones with activated leaving groups such as 4a (X ) OH) coupled efficiently with a broad range of nucleophiles.

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Synthesis of a Butyrolactone Precursor of an Algae Nonaether from an Enantiopure Glycol Obtained by Hoppe's Chemistry

Menges

Brückner

1998

Eur. J. Org. Chem.

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Oxidative Degradation of γ-Butyrolactons into 1,3-Diols via a Criegee Rearrangement of Peroxosulfonates. An Enantioselective Synthesis of Compactin Lactone and its Diastereomer

Cited by 26 publications

References 0 publications

Nonracemic γ‐Lactones from the Sharpless Asymmetric Dihydroxylation of β,γ‐Unsaturated Carboxylic Esters

Nonracemic γ‐Lactones from the Sharpless Asymmetric Dihydroxylation of β,γ‐Unsaturated Carboxylic Esters

Scope and Limitations in Palladium-Catalyzed Substitution Reactions of Unsaturated Fused Lactones

Synthesis of a Butyrolactone Precursor of an Algae Nonaether from an Enantiopure Glycol Obtained by Hoppe's Chemistry

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