Dehydrative glycosylation with cyclic phosphonium anhydrides

Dyapa, Rajendar; Dockery, Lance T.; Walczak, M

doi:10.1039/c6ob01812b

Cited by 24 publications

(18 citation statements)

References 60 publications

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“…Inspired by the work of Mukaiyama and seeking to increase the viability of phosphonium salt‐assisted dehydrative glycosylation, Walczak and co‐workers investigated the efficacy of cyclic phosphonium anhydride salts as C1‐OH activators (Scheme b) . Because of their broad functional group tolerance, convenient methods of formation, and facile modulation of structural and electronic properties, this class of reagents offers advantages over other dehydrative reagents.…”

Section: Direct C1‐hydroxy Activation Using Non‐acid Electrophilic Rementioning

confidence: 98%

Direct Dehydrative Glycosylation of C1‐Alcohols

O’Neill

Rodriguez

Walczak

2018

Chemistry An Asian Journal

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Due to the central role played by carbohydrates in a multitude of biological processes, there has been a sustained interest in developing effective glycosylation methods to enable more thorough investigation of their essential functions. Among the myriad technologies available for stereoselective glycoside bond formation, dehydrative glycosylation possesses a distinct advantage given the unique properties of C1-alcohols such as straightforward preparation, stability, and a general reactivity compatible with a diverse set of reaction conditions. In this Focus Review, a survey of direct dehydrative glycosylations of C1-alcohols is provided with an emphasis on recent achievements, pervading limitations, mechanistic insights, and applications in total synthesis.

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Section: Direct C1‐hydroxy Activation Using Non‐acid Electrophilic Rementioning

confidence: 98%

Direct Dehydrative Glycosylation of C1‐Alcohols

O’Neill

Rodriguez

Walczak

2018

Chemistry An Asian Journal

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“…Stereoselective glycosylation that involves the possible intermediacy of a phosphonium halide intermediate was first introduced by the Mukaiyama laboratory in 2003 . Codée and co‐workers applied this strategy to rescue the poor selectivity of the glycosylation between perbenzylated glucosyl donors and primary glucosyl acceptors (Scheme ) . Here, the addition of excess triphenylphosphine oxide gives the best results in terms of stereoselectivity.…”

Section: Stereoselective Glycosylation Modulatorsmentioning

confidence: 99%

“…Together with the DMF‐modulated glycosylation with secondary acceptors, Codée's group successfully synthesized a Mycobacterium tuberculosis derived branched nonasaccharide . Very recently, a phosphonium‐modulated glycosylation was also reported by Walczak's group, which achieved high α‐selectivity with arabinose donors …”

Section: Stereoselective Glycosylation Modulatorsmentioning

confidence: 99%

Recent Developments in Stereoselective Chemical Glycosylation

Ling

Bennett

2019

Asian J Org Chem

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Because of their pivotal biological functions, attention to sugars and glycobiology has grown rapidly in recent decades, leading to increased demand for homogeneous oligosaccharides. The stereoselective preparation of oligosaccharides by chemical means remains challenging and continues to be a vivid research area for organic chemists. In the past decade, new approaches and reinvestigated tradi-tional methods have transformed the field. These developments include novel catalyses, various types of glycosylation modulators and the use of photochemical energy to facilitate glycosylation. This Minireview presents a brief overview of the latest trends in chemical glycosylation, with emphasis on the stereoselective synthetic protocols developed in the past decade.[a] Dr.

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“…Anomeric stannanes are also compatible with classical glycosylation conditions: we demonstrated that Schmidt‐type donors activated using TMSOTf or Pd II catalysts can reliably extend the oligosaccharide chain using anomeric nucleophiles as glycosyl acceptors. Moreover, anomeric stannanes are tolerated under dehydrative glycosylation promoted by cyclic phosphonium anhydrides and 1,2‐anhydro‐sugars can also be efficiently converted into the corresponding 2‐OH glycosides using stannanes as the glycosyl acceptors . With these conditions in hand, we were able to prepare a series of linear and branched saccharides .…”

Section: Synthesis Of Anomeric Stannanesmentioning

confidence: 99%

Rethinking Carbohydrate Synthesis: Stereoretentive Reactions of Anomeric Stannanes

Zhu

O’Neill

Rodriguez

et al. 2018

Chemistry A European J

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In this Concept article, we highlight recent advances in the synthesis and applications of anomeric nucleophiles, a class of carbohydrates in which the C1 carbon bears a carbon-metal bond. First, we discuss the advantages of exploiting the carboanionic reactivity of carbohydrates and the methods for the synthesis of mono- and oligosaccharide stannanes. Second, we discuss recent developments in the glycosyl cross-coupling method resulting in transfer of anomeric configuration from C1 stannanes to C-aryl glycosides. These highly stereoretentive processes are ideally suited for the preparation of and was demonstrated in the synthesis of antidiabetic drugs. Next, we highlight the applications of glycosyl cross-coupling method to the preparation of Se-glycosides and in glycodiversification of small molecules and peptides. These reactions proceed with exclusive anomeric control for a broad range of substrates and tolerate carbohydrates with free hydroxyl groups. Taken together, anomeric nucleophiles have emerged as powerful tools for the synthesis of oligosaccharides and glycoconjugates and their future applications will open new avenues to incorporate saccharides into small molecules and biologics.

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Dehydrative glycosylation with cyclic phosphonium anhydrides

Cited by 24 publications

References 60 publications

Direct Dehydrative Glycosylation of C1‐Alcohols

Direct Dehydrative Glycosylation of C1‐Alcohols

Recent Developments in Stereoselective Chemical Glycosylation

Rethinking Carbohydrate Synthesis: Stereoretentive Reactions of Anomeric Stannanes

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