Leveraging Trifluoromethylated Benzyl Groups toward the Highly 1,2-<i>Cis</i>-Selective Glucosylation of Reactive Alcohols

Njeri, Dancan K.; Valenzuela, Erik Alvarez; Ragains, Justin R.

doi:10.1021/acs.orglett.1c02947

Cited by 10 publications

(10 citation statements)

References 35 publications

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“…Use of iodotrimethylsilane (TMS-I) as exogenous iodide source in the presence of triphenylphosphine oxide (TPPO) were further demonstrated by Njeri et al (2021 ). Glycosylation reaction of N -phenyltrifluroacetimidate donors ( 113 ) with various primary acceptors resulted their corresponding α-glycosides ( 114 ) in high yield and stereoselectivity (III in Scheme 10 ).…”

Section: Techniques For 12- Cis Glycosylation Reac...mentioning

confidence: 99%

Recent Advances in Stereoselective Chemical O-Glycosylation Reactions

Mukherjee

Ghosh

Hanover

2022

Front. Mol. Biosci.

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Carbohydrates involving glycoconjugates play a pivotal role in many life processes. Better understanding toward glycobiological events including the structure–function relationship of these biomolecules and for diagnostic and therapeutic purposes including tailor-made vaccine development and synthesis of structurally well-defined oligosaccharides (OS) become important. Efficient chemical glycosylation in high yield and stereoselectivity is however challenging and depends on the fine tuning of a protection profile to get matching glycosyl donor–acceptor reactivity along with proper use of other important external factors like catalyst, solvent, temperature, activator, and additive. So far, many glycosylation methods have been reported including several reviews also. In the present review, we will concentrate our discussion on the recent trend on α- and β-selective glycosylation reactions reported during the past decade.

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Section: Techniques For 12- Cis Glycosylation Reac...mentioning

confidence: 99%

Recent Advances in Stereoselective Chemical O-Glycosylation Reactions

Mukherjee

Ghosh

Hanover

2022

Front. Mol. Biosci.

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“…Recently, some practical methodologies have been reported. Additives such as DMF (Koto et al, 1984;Sato et al, 1986) and Ph 3 P=O were effectively used for the stereoselective construction of α-glucosyl linkages to secondary alcohols with TMSOTf and primary alcohols with TMSI, respectively (Wang et al, 2018;Njeri et al, 2021). The alternative nucleophilic additive for α-glycosylation methyl (phenyl) formamide (MPF) was found and applied to the synthesis of α-(1,4)-glucosamine and α-(1,4)-galactosamine linkages (Figure 2A4) (Wang et al, 2020;.…”

Section: Recent Advances On 12-cis Glycosylations By Intermolecular C...mentioning

confidence: 99%

Recent advances in stereoselective 1,2-cis-O-glycosylations

Ishiwata

Tanaka

et al. 2022

Front. Chem.

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For the stereoselective assembly of bioactive glycans with various functions, 1,2-cis-O-glycosylation is one of the most essential issues in synthetic carbohydrate chemistry. The cis-configured O-glycosidic linkages to the substituents at two positions of the non-reducing side residue of the glycosides such as α-glucopyranoside, α-galactopyranoside, β-mannopyranoside, β-arabinofuranoside, and other rather rare glycosides are found in natural glycans, including glycoconjugate (glycoproteins, glycolipids, proteoglycans, and microbial polysaccharides) and glycoside natural products. The way to 1,2-trans isomers is well sophisticated by using the effect of neighboring group participation from the most effective and kinetically favored C-2 substituent such as an acyl group, although high stereoselective synthesis of 1,2-cis glycosides without formation of 1,2-trans isomers is far less straightforward. Although the key factors that control the stereoselectivity of glycosylation are largely understood since chemical glycosylation was considered to be one of the useful methods to obtain glycosidic linkages as the alternative way of isolation from natural sources, strictly controlled formation of these 1,2-cis glycosides is generally difficult. This minireview introduces some of the recent advances in the development of 1,2-cis selective glycosylations, including the quite recent developments in glycosyl donor modification, reaction conditions, and methods for activation of intermolecular glycosylation, including the bimodal glycosylation strategy for 1,2-cis and 1,2-trans glycosides, as well as intramolecular glycosylations, including recent applications of NAP-ether-mediated intramolecular aglycon delivery.

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“…It is worth noting that other glycosylation methods oen failed to achieve highly stereoselective 1,2-cis glycosylation when highly reactive primary alcohols were used as strong nucleophile acceptors. [37][38][39][40][41][42][43] Glycosylation of carbohydrate acceptors 15g-m including Dglucopyranosyl, D-galactopyranosyl, D-mannopyranosyl and Darabinofuranosyl primary alcohols with 13h also proceeded smoothly, generating the corresponding disaccharides 16g-m in excellent yields (93-99%) as single a isomers. Carbohydrate secondary alcohols 15n-q including the hindered O4-position of glucose were also glycosylated efficiently with 13h, producing a-(1/4), (1/3), and (1/2)-disaccharides 16n-q in 87-97% yields with complete stereocontrol.…”

Section: Dft Calculationsmentioning

confidence: 99%