Reagent-Controlled α-Selective Dehydrative Glycosylation of 2,6-Dideoxy Sugars: Construction of the Arugomycin Tetrasaccharide

Romeo, Joseph R.; McDermott, Luca; Bennett, Clay S.

doi:10.1021/acs.orglett.0c01153

Cited by 13 publications

(11 citation statements)

References 75 publications

(98 reference statements)

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“…Dideoxygenated sugars are less common, but 2,6-dideoxy- and 3,6-dideoxysugars are important constituents of bioactive compounds including macrolide antibiotics and cardiac glycosides (e.g., digitoxose), which without the sugar group have reduced or no bioactivity. Their synthesis − and conformational analysis continue to be the subject of much study. Hexoses with dideoxygenation at the 4- and 6-positions are rarer sugars yet have been reported to play key roles in macrolide antibiotic pharmacokinetics, pharmacodynamics, and molecular target recognition. − Thorson et al recently described an elegant approach for the synthesis of all eight possible 2,3-diastereomers of 4,6-dideoxyhexoses in enantiomerically pure form from a single natural product source .…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Structural Characteristics of all Mono- and Difluorinated 4,6-Dideoxy-d-xylo-hexopyranoses

et al. 2021

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Protein–carbohydrate interactions are implicated in many biochemical/biological processes that are fundamental to life and to human health. Fluorinated carbohydrate analogues play an important role in the study of these interactions and find application as probes in chemical biology and as drugs/diagnostics in medicine. The availability and/or efficient synthesis of a wide variety of fluorinated carbohydrates is thus of great interest. Here, we report a detailed study on the synthesis of monosaccharides in which the hydroxy groups at their 4- and 6-positions are replaced by all possible mono- and difluorinated motifs. Minimization of protecting group use was a key aim. It was found that introducing electronegative substituents, either as protecting groups or as deoxygenation intermediates, was generally beneficial for increasing deoxyfluorination yields. A detailed structural study of this set of analogues demonstrated that dideoxygenation/fluorination at the 4,6-positions caused very little distortion both in the solid state and in aqueous solution. Unexpected trends in α/β anomeric ratios were identified. Increasing fluorine content always increased the α/β ratio, with very little difference between regio- or stereoisomers, except when 4,6-difluorinated.

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Section: Introductionmentioning

confidence: 99%

Synthesis and Structural Characteristics of all Mono- and Difluorinated 4,6-Dideoxy-d-xylo-hexopyranoses

et al. 2021

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“…Alternatively, the glycosylation of the corresponding d -fucosamine donor with PMPOH, followed by inversion at C4, would lead to 6 . Both d -bacillosamine and d -fucosamine thioglycoside donors are readily accessible in excellent overall yields through our established protocol via the sequential one-pot displacement of corresponding 2,4-bistriflates. , Recent work by Bennett and co-workers demonstrated that the 2-naphthylmethyl (Nap) group and PMP groups can be orthogonally cleaved to facilitate chain extension of the RUs in complex oligosaccharide assembly. Indeed, the reducing-end PMP ether can be easily cleaved using CAN to reveal the anomeric hemiacetal, which can be transformed into either a variety of donors for further attachment with a saccharide or a linker for protein conjugation …”

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confidence: 99%

Total Synthesis of the Repeating Units of O-Specific Polysaccharide of Pseudomonas chlororaphis subsp. aureofaciens UCM B-306 via One-Pot Glycosylation

et al. 2022

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Herein we report the first total syntheses of the trisaccharide-repeating units of Pseudomonas chlororaphis subsp. aureofaciens UCM B-306 via a one-pot assembly of the core trisaccharide structure. The rare-sugar-containing trisaccharide-repeating units are comprised of d-bacillosamine, 2-amino-2-deoxy-d-galacturonic acid or amide, and d-rhamnose units linked through three consecutive α-linkages. The total syntheses of two repeating units were completed starting from d-mannose via a longest-linear sequence of 27 steps in 5.8% and 4.4% overall yields, respectively.

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“…While efficient, the cost of 1 led to investigation of a more affordable and scalable route. To this end, a peracetylation, bromination, and Fischer–Zach sequence starting from commercially available l ‐rhamnose 11 was explored [52, 53] . After optimization of each reaction (SI, Section 2.2), telescoping the sequence was achieved by utilizing acetyl bromide to perform a tandem acetylation/bromination to generate a glycosyl bromide.…”

Section: Methodsmentioning

confidence: 99%

Automated, Multistep Continuous‐Flow Synthesis of 2,6‐Dideoxy and 3‐Amino‐2,3,6‐trideoxy Monosaccharide Building Blocks

et al. 2021

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An automated continuous flow system capable of producing protected deoxy‐sugar donors from commercial material is described. Four 2,6‐dideoxy and two 3‐amino‐2,3,6‐trideoxy sugars with orthogonal protecting groups were synthesized in 11–32 % overall yields in 74–131.5 minutes of total reaction time. Several of the reactions were able to be concatenated into a continuous process, avoiding the need for chromatographic purification of intermediates. The modular nature of the experimental setup allowed for reaction streams to be split into different lines for the parallel synthesis of multiple donors. Further, the continuous flow processes were fully automated and described through the design of an open‐source Python‐controlled automation platform.

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Reagent-Controlled α-Selective Dehydrative Glycosylation of 2,6-Dideoxy Sugars: Construction of the Arugomycin Tetrasaccharide

Cited by 13 publications

References 75 publications

Synthesis and Structural Characteristics of all Mono- and Difluorinated 4,6-Dideoxy-d-xylo-hexopyranoses

Synthesis and Structural Characteristics of all Mono- and Difluorinated 4,6-Dideoxy-d-xylo-hexopyranoses

Total Synthesis of the Repeating Units of O-Specific Polysaccharide of Pseudomonas chlororaphis subsp. aureofaciens UCM B-306 via One-Pot Glycosylation

Automated, Multistep Continuous‐Flow Synthesis of 2,6‐Dideoxy and 3‐Amino‐2,3,6‐trideoxy Monosaccharide Building Blocks

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