A Convenient, Highly Efficient One-Pot Preparation of Peracetylated Glycals From Reducing Sugars

Shull, Brian K.; Wu, Zhijun; Koreeda, Masato

doi:10.1080/07328309608005701

Cited by 87 publications

(48 citation statements)

References 22 publications

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“…Thus, a series of l-heptosylglycals 11-13 could be efficiently prepared by using a known zinc-mediated glycal formation, [20] followed by protective group manipulations.…”

Section: Synthesis Of Heptosylglycalsmentioning

confidence: 99%

Stereoselective Glycal Fluorophosphorylation: Synthesis of ADP‐2‐fluoroheptose, an Inhibitor of the LPS Biosynthesis

Dohi

Périon

Durka

et al. 2008

Chemistry A European J

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Heptosides are found in important bacterial glycolipids such as lipopolysaccharide (LPS), the biosynthesis of which is targeted for the development of novel antibacterial agents. This work describes the synthesis of a fluorinated analogue of ADP‐L‐glycero‐β‐D‐manno‐heptopyranose, the donor substrate of the heptosyl transferase WaaC, which catalyzes the incorporation of this carbohydrate into LPS. Synthetically, the key step for the preparation of ADP‐2F‐heptose is the simultaneous and stereoselective installation of both the fluorine atom at C‐2 and the phosphoryl group at C‐1 through a selectfluor‐mediated (selectfluor=1‐chloromethyl‐4‐fluorodiazoniabicyclo[2.2.2]octane bis(triflate)) electrophilic addition/nucleophilic substitution involving a heptosylglycal. Therefore, we detail in this article 1) the stereoselective preparation of the key intermediates heptosylglycals, 2) the development of a new fluorophosphorylation procedure allowing an excellent β‐gluco stereoselectivity with “all‐equatorial” glycals, 3) the synthesis of the target ADP‐2F‐heptose, and 4) some comments on the contacts observed between the fluorine atom of the final molecule and the protein in the crystallographic structure of heptosyltransferase WaaC.

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“…Thus, a series of l-heptosylglycals 11-13 could be efficiently prepared by using a known zinc-mediated glycal formation, [20] followed by protective group manipulations.…”

Section: Synthesis Of Heptosylglycalsmentioning

confidence: 99%

Stereoselective Glycal Fluorophosphorylation: Synthesis of ADP‐2‐fluoroheptose, an Inhibitor of the LPS Biosynthesis

Dohi

Périon

Durka

et al. 2008

Chemistry A European J

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“…[36,37] -Glucose was converted into the triacetylglucal 13a in 98% yield in a one-pot reaction via the 1-bromotetraacetate and reductive elimination with zinc. [38] The glucal was then deacylated with sodium methoxide in 96% yield to afford the glucal 13b. When the same reaction conditions were applied to galactose, the triacetylgalactal 14a was obtained in a lower yield of 53% yield [38] and deacylated to give 14b in 98% yield.…”

Section: Preparation Of Methyl Glycosidesmentioning

confidence: 99%

“…[38] The glucal was then deacylated with sodium methoxide in 96% yield to afford the glucal 13b. When the same reaction conditions were applied to galactose, the triacetylgalactal 14a was obtained in a lower yield of 53% yield [38] and deacylated to give 14b in 98% yield. With boron trifluoride؊diethyl ether in benzene/ methanol, 13a was transformed Ϫ by S N 2Ј substitution of the 3-acetoxy group by the methoxy group Ϫ into 15a in 90% yield.…”

Section: Preparation Of Methyl Glycosidesmentioning

confidence: 99%

TEMPO‐Mediated Anodic Oxidation of Methyl Glycosides and 1‐Methyl and 1‐Azido Disaccharides

Schämann

Schäfer

2002

Eur J Org Chem

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Methyl glycosides of L‐sorbopyranoside, D‐fructopyranoside, D‐glucosaminopyranoside, 2,3‐dehydro‐2,3‐dideoxyglucopyranoside, cellobiose, lactose, and maltose and the 1‐azido derivatives of glucose, cellobiose, lactose, and maltose have been converted into the corresponding uronic acids in moderate to excellent yields by TEMPO‐mediated anodic oxidation. The anode proves to be an advantageous alternative to other cooxidants in TEMPO+ oxidations of carbohydrates and is compatible with N‐acylamino and azido groups and with double bonds. The electrolyte, a carbonate buffer, can easily be removed with a cation‐exchange resin, a facile scale‐up by increasing the electrode area is possible. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

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“…Due to their enol ether structure, they show interesting reactivities that have proven useful in target molecule synthesis, beyond carbohydrate chemistry. [14][15][16] While most glycal syntheses rely on reductive elimination of glycosides in one way or the other, [17,18] over the past few years transition metal mediated or catalyzed cyclization reactions became more and more important. In particular, the cyclization of alkynols [19][20][21] and the ring-closing metathesis [22][23][24] of enol ethers [25][26][27][28][29] has attracted considerable attention.…”

Section: Introductionmentioning

confidence: 99%

The Tandem Ring‐Closing Metathesis–Isomerization Approach to 6‐Deoxyglycals

Schmidt

Biernat

2008

Chemistry A European J

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Protected 3,6-dideoxyglycals have been synthesized de novo as single isomers starting from ethyl lactate by using the tandem RCM-isomerization reaction as the key step. Different relative configurations become accessible by addition of vinyl- or allyl-metal compounds to protected lactaldehydes under Cram-chelate or Felkin-Anh control. The concept is exemplified for glycals of L-rhodinose and L-amicetose, as well as for ring-expanded non-natural analogues thereof. This novel approach to glycals is also applicable to the synthesis of disaccharide glycals via a reiterative strategy, as exemplified for the dimer of L-rhodinose and its non-natural ring expanded analogue.

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A Convenient, Highly Efficient One-Pot Preparation of Peracetylated Glycals From Reducing Sugars

Cited by 87 publications

References 22 publications

Stereoselective Glycal Fluorophosphorylation: Synthesis of ADP‐2‐fluoroheptose, an Inhibitor of the LPS Biosynthesis

Stereoselective Glycal Fluorophosphorylation: Synthesis of ADP‐2‐fluoroheptose, an Inhibitor of the LPS Biosynthesis

TEMPO‐Mediated Anodic Oxidation of Methyl Glycosides and 1‐Methyl and 1‐Azido Disaccharides

The Tandem Ring‐Closing Metathesis–Isomerization Approach to 6‐Deoxyglycals

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