Stereoselective synthesis of 2′-modified nucleosides by using ortho-alkynyl benzoate as a gold(<scp>i</scp>)-catalyzed removable neighboring participation group

Ding, Haixin; Li, Chuang; Zhou, Yirong; Hong, Sheng; Zhang, Ning; Xiao, Qiang

doi:10.1039/c6ra27790j

Cited by 5 publications

(7 citation statements)

References 31 publications

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“…The strong electronwithdrawing effect of the 2-fluoride atom meant that 6amino-2-fluoroadenine did not interfere with the activity of the Au(I) catalysis, which was found to deactivate the catalysis in adenine and cystine as nucleobases. 14 In addition, a single crystal suitable for X-ray crystallography of nucleoside 12b was obtained and the structure was unambiguously confirmed (Figure 2; CCDC 1938040). 18 As shown, the sugar puckering adopted a rare C-2′ endo-configuration, which is locked by the hydrogen bond between C-2′ OH and the carbonyl of the pivaloyl group.…”

Section: Syn Thesismentioning

confidence: 92%

“…Next, the 2′-ortho-alkyne-benzoyl nucleoside 11 was subjected to deprotection by using the previously developed method (5 mol% freshly prepared Ph 3 PAuOTFA with 1 equiv H 2 O and 6 equiv EtOH). 14 The reaction proceeded smoothly to afford 2′-OH nucleosides 12 with yields over 90%. The potential transesterification of the 3′-OH benzoyl group to 2′-OH was not observed.…”

Section: Syn Thesismentioning

confidence: 99%

“…Based on these criteria, we have successfully developed a novel ortho-alkynylbenzoate as a 2′-OH protecting group, which can be removed smoothly under the catalysis of Au(I) complexes with high yield and high selectivity (Scheme 1; this work, nucleoside 7 to nucleoside 8). 14 The reaction conditions are neutral and extraordinary mild.…”

Section: >90% Yieldsmentioning

confidence: 99%

“…Subsequent Sonogashira reaction with 1-hexyne gave ribose 10 in 74% yield in two steps using Pd(Ph 3 P) 2 Cl 2 and CuI as catalyst. 14 This protocol has been applied on a 100 gram scale successfully without column chromatography.…”

Section: >90% Yieldsmentioning

confidence: 99%

“…Supporting information for this article is available online at https://doi.org/10.1055/s-0039-1690732. Included are NMR spectra for compounds 1, 2, (11-14)a, (11)(12)(13)(14)b, and crystal data and structure refinement for 12b and 13a. S u p p o r t i n g I n f o r m a t i o n S u p p o r t i n g I n f o r m a t i o n C. Shen et al…”

Section: Funding Informationmentioning

confidence: 99%

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Practical Synthesis of Fludarabine and Nelarabine

Shen¹,

Liu²,

Ouyang³

et al. 2019

Synthesis

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A new practical synthesis strategy has been developed to access the β-d-arabinofuranosyl purine nucleosides fludarabine and nelarabine. In our approach, an ortho-alkyne benzoyl ester is transiently introduced as a neighbouring-participation group in Vorbrüggen glycosylation to afford the corresponding β-nucleoside exclusively. The latter was further removed efficiently by using freshly prepared Ph3PAuOTFA to give the corresponding 2′-OH nucleosides without transesterification. After reversion of the configuration of 2′-OH and deprotection, fludarabine and nelarabine were obtained in high yield and purity.

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Section: Syn Thesismentioning

confidence: 92%

Section: Syn Thesismentioning

confidence: 99%

Section: >90% Yieldsmentioning

confidence: 99%

Section: >90% Yieldsmentioning

confidence: 99%

Section: Funding Informationmentioning

confidence: 99%

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Practical Synthesis of Fludarabine and Nelarabine

Shen¹,

Liu²,

Ouyang³

et al. 2019

Synthesis

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Homogeneous Catalysis: A Powerful Technology for the Modification of Important Biomolecules

Shelke

Yashmeen

Gholap

et al. 2018

Chemistry An Asian Journal

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Homogeneous catalysis plays an important and ubiquitous role in the synthesis of simple and complex molecules, including drug compounds, natural products, and agrochemicals. In recent years, the wide-reaching importance of homogeneous catalysis has made it an indispensable tool for the modification of biomolecules, such as carbohydrates (sugars), amino acids, peptides, nucleosides, nucleotides, and steroids. Such a synthetic strategy offers several advantages, which have led to the development of new molecules of biological relevance at a rapid rate relative to the number of available synthetic methods. Given the powerful nature of homogeneous catalysis in effecting these synthetic transformations, this Focus Review has been compiled to highlight these important developments.

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