One-Pot Synthesis of 2-Deoxy-β-oligosaccharides

Pongdee, Rongson; Wu, Bin; Sulikowski, Gary A.

doi:10.1021/ol016593f

Cited by 62 publications

(35 citation statements)

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“…The past couple of years have seen significant advances in oligosaccharide synthesis, for example strategies for the synthesis of challenging 2-deoxy-b-glycosidic linkages, [10] solidphase approaches that may enable future automation, [11] and chemoenzymatic preparation by using engineered glycosynthases. [12] However, none of these embraces an aglycon backbone of pharmaceutically relevant drugs.…”

Section: Introductionmentioning

confidence: 99%

“…[3,8] Increasing the length or steric bulk of the N-acyl side chain of 1 a decreases cell-surface expression of the corresponding sialic acids. [10] A rate-determining step in the de novo biosynthesis of unnatural sialic acids appears to be the phosphorylation of ManNAc at the 6-OH by ManNAc 6-kinase. [10] Accordingly, Reutter and co-workers were able to introduce a Keywords: biosynthesis ¥ drug design ¥ enzymes ¥ glycosyltransferase ¥ urdamycin…”

Section: Introductionmentioning

confidence: 99%

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Rational Saccharide Extension by Using the Natural Product Glycosyltransferase LanGT4

et al. 2004

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Rational Saccharide Extension by Using the Natural Product Glycosyltransferase LanGT4

et al. 2004

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“…XVII 583 observed depending on the duration of the Zemplén saponification procedure. This compound would be ideally suited for further attachment of deoxysugars, for instance employing the selective a-glycoside synthesis using 2-deoxyglycosyl phosphates as proposed by Hashimoto [32] and recently employed by Sulikowski et al [33] In summary, the regioselective NBS bromination of the tetraacetate 7 allowed the large-scale preparation of the quinoid D-olivose-C-glycoside 8. The aglycone was constructed by Diels -Alder reaction and the stereoselective a-L-rhodinose-O-glycoside by using monoalcohol 15 and L-benzoylrhodinal (16) and scandium triflate as the promotor.…”

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confidence: 99%

“…The spectral data were in agreement with those published by Toshima et al [16] Anal. Calcd for C 33 [16,24,28] to afford the fluoride 12 (390 mg, 60%). The spectral data were identical to those reported.…”

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confidence: 99%

Total Synthesis of Angucyclines. XVII. First Synthesis of Antibiotic 100‐1, a Deoxydisaccharide Angucycline Antibiotic of the Urdamycinone B‐Type

Krohn

Agócs

Bäuerlein

2003

Journal of Carbohydrate Chemistry

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Two routes to the deoxydisaccharide angucycline antibiotic 100-1 (3) are described. Key steps comprise the regioselective oxidation/bromination of the 1,5-diacetoxyolivose C-saccharide 7 to the bromoquinone 8. Diels -Alder reaction of the bromoquinone with the diene 9 followed by HBr elimination afforded the urdamycinone B precursor 11 as a diastereomeric mixture. Selective protection as the TBDMS ether 13, acetylation and deprotection of the silyl ether afforded the alcohol 15 which was selectively glycosylated to the a-rhamnal glycoside 17 in 72% yield (at 70% conversion) using benzoyl rhamnal (16) as the glycoside donor and scandium triflate as the promotor. The silyl group at C-3 of the aglycone was then transformed into a hydroxyl group. Zemplén deacylation and photooxidation of the benzylic position at C-1 then converted the two diastereoisomers into the natural product 3 and the C-3 diastereoisomer 20. At this stage the diastereomers 3 and 20 were separated. Alternatively and more easily, the diastereomers were separated at the stage of the urdamycinone B analogues 21a and 21b, followed by a similar reaction sequence to the natural disaccharide 3.

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“…However, one of the barriers preventing effective production of an anticancer vaccine is the limited supply of chemically pure Fuc-GM 1 oligosaccharide. Despite the development of various oligosaccharide synthetic methods (5)(6)(7)(8), the first synthesis of Fuc-GM 1 glycoside was reported by Allen and Danishefsky (9) two decades after its initial discovery. This elegant strategy incorporated the sulfonamide glycosidation method (10) in conjunction with a [3 ϩ 3] convergent glycosylation, ultimately leading to the target glycoside.…”

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Reactivity-based one-pot total synthesis of fucose GM ₁ oligosaccharide: A sialylated antigenic epitope of small-cell lung cancer

Mong

Lee

Durón

et al. 2003

Proc. Natl. Acad. Sci. U.S.A.

127

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The total synthesis of the sialic acid-containing antigenic epitope fucose GM1 (Fuc-GM1) by an improved reactivity-based one-pot synthetic strategy is reported. Based on a thioglycoside reactivity database, three saccharide building blocks, 3, 4, and 5, were designed and prepared to incorporate a descending order of reactivity toward thiophilic activation. Using the reactivity-based one-pot synthetic method, the fully protected Fuc-GM1 glycoside 2 was furnished in a facile manner, which was globally deprotected to give the Fuc-GM1 glycoside 1. In addition, using the promoter system 1-(benzensulfinyl)piperidine͞trifluoromethanesulfonic anhydride, the product yield was improved and the reaction time was reduced in comparison with the N-iodosuccinimide͞trifluoro-methanesulfonic acid-and dimethyl (thiomethyl) sulfonium trifluoromethanesulfonate-promoted systems.synthetic vaccine F ucose GM 1 (Fuc-GM 1 ) ganglioside was first isolated from bovine thyroid tissue in 1979 (1). It is comprised of a hexasaccharide carbohydrate moiety and a ceramide-reducing end component. Within this carbohydrate framework is a tetrasaccharide (sugars a, b, d, and e) bearing a branched sialic acid residue (c) and a terminal fucose (f) (Fig. 1). It is found specifically in the tumor tissue of small-cell lung cancer (SCLC). SCLC accounts for 20% of lung cancer, which remains one of the leading causes of death in the United States (2). Unlike other cancer antigens, Fuc-GM 1 has a more restricted distribution in normal tissue, suggesting that this carbohydrate antigen may be a good target for active immunization. Development of an anti-(Fuc-GM 1 ) vaccine and mAb could potentially be of importance for diagnosis and immunotherapy of these tumors (3, 4). However, one of the barriers preventing effective production of an anticancer vaccine is the limited supply of chemically pure Fuc-GM 1 oligosaccharide. Despite the development of various oligosaccharide synthetic methods (5-8), the first synthesis of Fuc-GM 1 glycoside was reported by Allen and Danishefsky (9) two decades after its initial discovery. This elegant strategy incorporated the sulfonamide glycosidation method (10) in conjunction with a [3 ϩ 3] convergent glycosylation, ultimately leading to the target glycoside. It required protecting group and anomeric leaving group manipulations and encountered a problem with stereoselective formation of the ␤(1,4) glycosidic bond between a bulky trisaccharide donor and the poor nucleophilic trisaccharide acceptor.We envisioned that the incorporation of our programmable reactivity-based one-pot strategy (8) in the synthesis of the Fuc-GM 1 could simplify this complicated synthetic operation. In brief, the reactivity-based one-pot strategy is based on a developed competitive HPLC assay to assess quantitatively the reactivity of different thioglycosides, the so-called relative reactivity value (RRV). Such information is then used to guide the reactivity-based one-pot synthesis of an oligosaccharide without protecting group manipulation and intermed...

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One-Pot Synthesis of 2-Deoxy-β-oligosaccharides

Abstract: [reaction: see text]. A new one-pot method using glycosyl phosphites for the synthesis of 2-deoxy-beta-oligosaccharides is described.

Cited by 62 publications

References 23 publications

Rational Saccharide Extension by Using the Natural Product Glycosyltransferase LanGT4

Rational Saccharide Extension by Using the Natural Product Glycosyltransferase LanGT4

Total Synthesis of Angucyclines. XVII. First Synthesis of Antibiotic 100‐1, a Deoxydisaccharide Angucycline Antibiotic of the Urdamycinone B‐Type

Reactivity-based one-pot total synthesis of fucose GM ₁ oligosaccharide: A sialylated antigenic epitope of small-cell lung cancer

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One-Pot Synthesis of 2-Deoxy-β-oligosaccharides

Abstract: [reaction: see text]. A new one-pot method using glycosyl phosphites for the synthesis of 2-deoxy-beta-oligosaccharides is described.

Cited by 62 publications

References 23 publications

Rational Saccharide Extension by Using the Natural Product Glycosyltransferase LanGT4

Rational Saccharide Extension by Using the Natural Product Glycosyltransferase LanGT4

Total Synthesis of Angucyclines. XVII. First Synthesis of Antibiotic 100‐1, a Deoxydisaccharide Angucycline Antibiotic of the Urdamycinone B‐Type

Reactivity-based one-pot total synthesis of fucose GM 1 oligosaccharide: A sialylated antigenic epitope of small-cell lung cancer

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Reactivity-based one-pot total synthesis of fucose GM ₁ oligosaccharide: A sialylated antigenic epitope of small-cell lung cancer