Direct <i>N</i>‐Glycofunctionalization of Amides with Glycosyl Trichloroacetimidate by Thiourea/Halogen Bond Donor Co‐Catalysis

Kobayashi, Yusuke; Nakatsuji, Yuya; Li, Shanji; Tsuzuki, Seiji; Takemoto, Yoshiji

doi:10.1002/ange.201712726

Cited by 25 publications

(8 citation statements)

References 82 publications

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“…To our delight, gold catalyzed glycosidation was found to be suitable for the direct attachment of the asparagine derivative 6 a emulating the biosynthetic machinery of N ‐linked glycoprotein synthesis. The protected asparagine Cbz⋅Asn⋅OBn ( 10 ) produced the N ‐linked asparagine ribofuranoside 11 a in 75 % yield within 3 h directly without any formation of the 1,6‐anhydro sugar [9b] or the orthoamides as reported earlier [9c] . Identification of these silver‐assisted gold‐catalyzed N ‐glycosidation conditions for the model ribofuranosides 1 a → 4 a , 7 a , 9 a , 11 a motivated us to investigate the scope of these glycosidation conditions for the synthesis of a range of N ‐glycosides.…”

Section: Figuresupporting

confidence: 55%

Synthesis of N‐Glycosides by Silver‐Assisted Gold Catalysis

et al. 2022

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The synthesis of N-glycosides from stable glycosyl donors in a catalytic fashion is still challenging, though they exist ubiquitously in DNA, RNA, glycoproteins, and other biological molecules. Herein, silverassisted gold-catalyzed activation of alkynyl glycosyl carbonate donors is shown to be a versatile approach for the synthesis of purine and pyrimidine nucleosides, asparagine glycosides and quinolin-2-one N-glycosides. Thus synthesized nucleosides were subjected to the oxidation-reduction sequence for the conversion of Ribf-into Araf-nucleosides, giving access to nucleosides that are otherwise difficult to synthesize. Furthermore, the protocol is demonstrated to be suitable for the synthesis of 2'-modified nucleosides in a facile manner. Direct attachment of an asparagine-containing dipeptide to the glucopyranose and subsequent extrapolation to afford the dipeptide disaccharide unit of chloroviruses is yet another facet of this endeavor.

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Section: Figuresupporting

confidence: 55%

Synthesis of N‐Glycosides by Silver‐Assisted Gold Catalysis

et al. 2022

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“…[42,43] Though, rearrangement of trichloroacetimidates to trichloroacetamides is a known side reaction. [44] A working hypothesis that could explain this anomerization is that after protonation and formation of an oxocarbenium ion-like intermediate, the acceptor will not be in a favourable trajectory for attack of the anomeric carbon (Figure 4). Whereby reattachment of the amide becomes a competing pathway.…”

Section: P E R S O N a L A C C O U N T T H E C H E M I C A L R E C O R Dmentioning

confidence: 99%

Self‐Promoted Stereoselective Glycosylations – Past, Present, Future

Faurschou

Pedersen

2021

The Chemical Record

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Self‐promoted glycosylations have generally not received much attention, despite having the advantages of being easy to perform and often highly stereoselective. This account covers the work done in this field and the mechanistic aspects of self‐promoted glycosylations are discussed, with a main focus on the stereoselectivity of the reactions. Most self‐promoted glycosylations utilize trichloroacetimidate donors, but examples of self‐promoted reactions with other donors have been described and will be discussed. Self‐promoted glycosylation strategies can provide a basis for new stereoselective glycosylation methodologies.

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“…Ribonucleoside syntheses are similarly well established, where typical methods utilize either a Lewis acid‐mediated (TiCl 4 ) chlorination of 1‐O‐acetyl‐2,3,5‐tri‐O‐benzoyl‐β‐ D ‐ribofuranose (Harki et al., ) or utilize intermediates 5 (Kane & Mann, ; Stewart & Williams, ) and 6 (Rosemeyer & Seela, ; Ugarkar et al., ; Wilcox & Otoski, ). We found that displacement of 1‐chloro‐2,3,5‐tri‐O‐benzoyl‐β‐ D ‐ribofuranose with the sodium salt of 4CI yielded what is likely a trapped amide acetal intermediate indicating a lack of nucleophilicity and thus did not produce the desired coupling product (see Kobayashi, Nakatsuji, Li, Tsuzuki, & Takemoto, and Sokolova, Shevchenko, & Preobrazhenskaya, for examples of such structures). We therefore chose to use the 5 / 6 sequence.…”

Section: Commentarymentioning

confidence: 99%

Synthesis of 4‐Cyanoindole Nucleosides, 4‐Cyanoindole‐2ʹ‐Deoxyribonucleoside‐5ʹ‐Triphosphate (4CIN‐TP), and Enzymatic Incorporation of 4CIN‐TP into DNA

Passow

Antczak

Sturla

et al. 2020

CP Nucleic Acid Chemistry

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4‐Cyanoindole‐2ʹ‐deoxyribonucleoside (4CIN) is a fluorescent isomorphic nucleoside analogue with superior spectroscopic properties in terms of Stokes shift and quantum yield in comparison to the widely utilized isomorphic nucleoside analogue, 2‐aminopurine‐2ʹ‐deoxyribonucleoside (2APN). Notably, when inserted into single‐ or double‐stranded DNA, 4CIN experiences substantially less in‐strand fluorescence quenching compared to 2APN. Given the utility of these properties for a spectrum of research applications involving oligonucleotides and oligonucleotide‐protein interactions (e.g., enzymatic processes, DNA hybridization, DNA damage), we envision that additional reagents based on 4‐cyanoindole nucleosides may be widely utilized. This protocol expands on the previously published synthesis of 4CIN to include synthetic routes to both 4‐cyanoindole‐ribonucleoside (4CINr) and 4‐cyanoindole‐2ʹ‐deoxyribonucleoside‐5ʹ‐triphosphate (4CIN‐TP), as well as a method for the enzymatic incorporation of 4CIN‐TP into DNA by a polymerase. These methods are anticipated to further enable the utilization of 4CIN in diverse applications involving DNA and RNA oligonucleotides. © 2020 by John Wiley & Sons, Inc. Basic Protocol 1: Synthesis of 4‐cyanoindole‐2ʹ‐deoxyribonucleoside (4CIN) and 4CIN phosphoramidite 4 Basic Protocol 2: Synthesis of 4‐cyanoindole‐ribonucleoside (4CINr) Basic Protocol 3: Synthesis of 4‐cyanoindole‐2ʹ‐deoxyribonucleoside‐5ʹ‐triphosphate (4CIN‐TP) Basic Protocol 4: Steady state incorporation kinetics of 2AP‐TP and 4CIN‐TP by a DNA polymerase

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Direct N‐Glycofunctionalization of Amides with Glycosyl Trichloroacetimidate by Thiourea/Halogen Bond Donor Co‐Catalysis

Cited by 25 publications

References 82 publications

Synthesis of N‐Glycosides by Silver‐Assisted Gold Catalysis

Synthesis of N‐Glycosides by Silver‐Assisted Gold Catalysis

Self‐Promoted Stereoselective Glycosylations – Past, Present, Future

Synthesis of 4‐Cyanoindole Nucleosides, 4‐Cyanoindole‐2ʹ‐Deoxyribonucleoside‐5ʹ‐Triphosphate (4CIN‐TP), and Enzymatic Incorporation of 4CIN‐TP into DNA

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