Widely Applicable Deprotection Method of 2,2,2-Trichloroethoxycarbonyl (Troc) Group Using Tetrabutylammonium Fluoride

Huang, Cheng Yuan; Wang, Ning; Fujiki, Katsumasa; Otsuka, Yuji; Akamatsu, Masao; Fujimoto, Yukari; Fukase, Koichi

doi:10.1080/07328303.2010.512405

Cited by 29 publications

(8 citation statements)

References 10 publications

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“…With the protected N -glycan 29 in hand, global deprotection of 29 was carried out (Scheme ). Cleavage of the N -Troc group with aqueous LiOH was identified by our research group . This method appeared to be applicable to the dodecasaccharide-Asn 29 ; however, our investigation suggested that aspartimide formed under basic conditions.…”

Section: Resultsmentioning

confidence: 75%

“…Cleavage of the N-Troc group with aqueous LiOH was identified by our research group. 85 This method appeared to be applicable to the dodecasaccharide-Asn 29; however, our investigation suggested that aspartimide formed under basic conditions. This side reaction was expected to occur via nucleophilic attack by the nitrogen in the side chain on the allyl ester.…”

Section: ■ Introductionmentioning

confidence: 72%

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Chemical Synthesis of a Complex-Type N-Glycan Containing a Core Fucose

et al. 2016

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A chemical synthesis of a core fucose containing N-glycan was achieved. Asparagine was introduced at an early stage of the synthesis, and the sugar chain was convergently elongated. As for the fragment synthesis, we reinvestigated α-sialylation, β-mannosylation, and N-glycosylation to reveal that precise temperature control was essential for these glycosylations. Intermolecular hydrogen bonds involving acetamide groups were found to reduce the reactivity in glycosylations: the protection of NHAc as NAc dramatically improved the reactivity. The dodecasaccharide-asparagine framework was constructed via the (4 + 4) glycosylation and the (4 + 8) glycosylation using the tetrasaccharide donor and the tetrasaccharide-asparagine acceptor. An ether-type solvent enhanced the yields of these key glycosylations between large substrates. After the whole deprotection of the dodecasaccharide, the target N-glycan was obtained.

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Section: Resultsmentioning

confidence: 75%

Section: ■ Introductionmentioning

confidence: 72%

Chemical Synthesis of a Complex-Type N-Glycan Containing a Core Fucose

et al. 2016

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“…The benzyl protection was left untouched at this stage of the synthesis to aid in the separation of products by HPLC after enzymatic modifications. Deprotection of the N‐Troc functionality under standard conditions with LiOH or zinc/acetic acid amalgam failed to provide clean products but refluxing the compounds 9 and 10 in 1 m TBAF in THF afforded the clean S. mansoni core 11 in 95 % and the mucin core 2 trisaccharide 12 in 78 % yield after three steps …”

Section: Resultsmentioning

confidence: 99%

Chemo‐Enzymatic Synthesis of S. mansoni O‐Glycans and Their Evaluation as Ligands for C‐Type Lectin Receptors MGL, DC‐SIGN, and DC‐SIGNR

Pham

Hernandez

Cioce

et al. 2020

Chemistry A European J

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Due to their interactions with C‐type lectin receptors (CLRs), glycans from the helminth Schistosoma mansoni represent promising leads for treatment of autoimmune diseases, allergies or cancer. We chemo‐enzymatically synthesized nine O‐glycans based on the two predominant O‐glycan cores observed in the infectious stages of schistosomiasis, the mucin core 2 and the S. mansoni core. The O‐glycans were fucosylated next to a selection of N‐glycans directly on a microarray slide using a recombinant fucosyltransferase and GDP‐fucose or GDP‐6‐azidofucose as donor. Binding assays with fluorescently labelled human CLRs DC‐SIGN, DC‐SIGNR and MGL revealed the novel O‐glycan O8 as the best ligand for MGL from our panel. Significant binding to DC‐SIGN was also found for azido‐fucosylated glycans. Contrasting binding specificities were observed between the monovalent carbohydrate recognition domain (CRD) and the tetravalent extracellular domain (ECD) of DC‐SIGNR.

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“…Allyl cleavage of 47 with palladium gave carboxylic acid 48. [28] After removal of all acyl and Troc groups under basic conditions, [29] acetyl groupsw ere introducedi nto the amino groups. Hydrogenation, followed by Fmoc protection of the amino group of asparagine afforded desired bisecting GlcNAc-con-tainingN -glycan 1 in 53 %y ield over4steps.…”

Section: Resultsmentioning

confidence: 99%

Convergent Synthesis of a Bisecting N‐Acetylglucosamine (GlcNAc)‐Containing N‐Glycan

Manabe

Shomura

Minamoto

et al. 2018

Chemistry An Asian Journal

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The chemical synthesis of a bisecting N-acetylglucosamine (GlcNAc)-containing N-glycan was achieved by a convergent synthetic route through [4+2] and [6+2] glycosylations. This synthetic route reduced the number of reaction steps, although the key glycosylations were challenging in terms of yields and selectivities owing to steric hindrance at the glycosylation site and a lack of neighboring group participation. The yields of these glycosylations were enhanced by stabilizing the oxocarbenium ion intermediate through ether coordination. Glycosyl donor protecting groups were explored in an effort to realize perfect α selectivity by manipulating remote participation. The simultaneous glycosylations of a tetrasaccharide with two disaccharides was investigated to efficiently construct a bisecting GlcNAc-containing N-glycan.

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Widely Applicable Deprotection Method of 2,2,2-Trichloroethoxycarbonyl (Troc) Group Using Tetrabutylammonium Fluoride

Cited by 29 publications

References 10 publications

Chemical Synthesis of a Complex-Type N-Glycan Containing a Core Fucose

Chemical Synthesis of a Complex-Type N-Glycan Containing a Core Fucose

Chemo‐Enzymatic Synthesis of S. mansoni O‐Glycans and Their Evaluation as Ligands for C‐Type Lectin Receptors MGL, DC‐SIGN, and DC‐SIGNR

Convergent Synthesis of a Bisecting N‐Acetylglucosamine (GlcNAc)‐Containing N‐Glycan

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