Highly Efficient Method for C-5 Halogenation of Pyrimidine-Based Nucleosides in Ionic Liquids

Kumar, Vineet; Yap, Jeremy L.; Muroyama, Andrew; Malhotra, Sanjay V.

doi:10.1055/s-0029-1217042

Cited by 8 publications

(2 citation statements)

References 30 publications

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“…An efficient, convenient, and benign methodology for C-5 halogenation of pyrimidine-based nucleosides has been developed by using N-halosuccinimides as halogenating reagents without any catalyst but with an expensive ionic liquid medium as a solvent. 17 Moreover, highly regioselective bromination of heteroaromatic compounds has been reported by using N-bromosuccinimide in tetrabutylammonium bromide. 18 Thus, the development of an affordable and simple protocol for efficiently synthesizing 5-halouracil derivatives is an attractive challenge.…”

Section: Letter Synlettmentioning

confidence: 99%

BF3@K10: An Efficient Heterogeneous Montmorillonite Catalyst for the Halogenation of N-Heterocycles

Lazrek,

El Mansouri,

Lachhab

et al. 2023

Synlett

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Halogenated N-heterocycles are an essential structural building-block in medicinal chemistry. Herein, we describe an economical and efficient protocol for regioselective halogenation of several N-heterocycles (pyrimidines, pyrazole, 2-aminopyridine, theophylline and imidazo[1,2-a]pyridine) using BF3 doped montmorillonite (BF3@K10). The new catalyst was characterized by FTIR, 11B NMR, XRD, SEM and EDS spectroscopy. The developed strategy provides easy and fast access to iodo-, bromo-, and chloro- N-heterocycles under mild conditions. The developed strategy is used to synthesized nine new halogenated derivatives of pyrimidines. This reaction under conventional heating or microwave conditions is simple, general, affording good to excellent yields of products, in the presence of BF3@K10 as an eco-friendly, inexpensive, and efficient catalyst, this reaction is simple and affording good to excellent yields of products under conventional heating or microwave conditions. This protocol is clearly superior to conventional route offering short reaction times, high yields, and easy workup..

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Section: Letter Synlettmentioning

confidence: 99%

BF3@K10: An Efficient Heterogeneous Montmorillonite Catalyst for the Halogenation of N-Heterocycles

Lazrek,

El Mansouri,

Lachhab

et al. 2023

Synlett

View full text Add to dashboard Cite

show abstract

“…Literature procedures inform about various methodologies for the bromination of pyrimidine moieties. Reaction of pyrimidine nucleosides with Br 2 /water (Fukuhara and Visser, 1951), Br 2 /CCl 4 (Fukuhara and Visser, 1955), Br 2 /CCl 4 in solvent mixture of anhydrous acetic acid and pyridine (Frisch and Visser, 1959), Br 2 /dimethylformamide (DMF; Duval and Ebel, 1964), N-bromosuccinimide (NBS) in DMF (Srivastava and Nagpal, 1970), m-chloroperbenzoic acid (MCPBA)/HBr in dimethylacetate (DMA) or DMF (Ryu and MacCoss, 1981), ceric ammonium nitrate (CAN)/LiBr in acetic acid or acetonitrile (Asakura and Robins, 1990), N-bromosuccinimide (NBS)/sodium azide (NaN 3 ) in dimethoxyethane (DME; Kumar et al, 1994), KBr/potassium monoperoxysulfate under aqueous conditions (Ross and Burrows, 1997), and NBS in ionic liquids (Kumar et al, 2009) are some of the reaction conditions developed. Bromination of C-8 of purine moieties has been achieved by various reaction conditions, such as Br 2 in glacial acetic acid/sodium acetate (Holmes and Robins, 1964), NBS in DMF (Srivastava and Nagpal, 1970), Br 2 in sodium acetate/dioxane (Clima and Bannwarth, 2008), and Br 2 in sodium acetate buffer (Ohkubo et al, 2011;Ghanty et al, 2012).…”

Section: Introductionmentioning

confidence: 99%

Facile Access to Bromonucleosides Using Sodium Monobromoisocyanurate (SMBI)

Maity

Srivastava

Sanghvi³

et al. 2017

CP Nucleic Acid Chemistry

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Bromonucleosides constitute a significant class of molecules and are well known for their biological activity. 5-Bromouridine, 5-bromo-2'-deoxyuridine, 5-bromouridine-5'-triphosphate, and nucleotides containing 5-bromouridine have been tested and used for numerous biological studies. 8-Bromopurine nucleosides have been used as essential precursors for the synthesis of nucleosides with fluorescent properties. This unit describes protocols for the synthesis of bromonucleosides using sodium monobromoisocyanurate (SMBI) in a straightforward way. Reactions are carried out at room temperature, and aqueous solvent mixtures are used to dissolve the nucleosides. Sodium azide is used as catalyst for the bromination of pyrimidine nucleosides, and no catalyst is necessary for the bromination of purine nucleosides. Unprotected 2'-deoxy pyrimidine and 2'-deoxy purine nucleosides are treated with SMBI to afford C-5 bromo pyrimidine and C-8 bromo purine nucleosides, respectively. This methodology has been found to be efficient for the synthesis of bromonucleosides on gram scale with consistently high yields. © 2017 by John Wiley & Sons, Inc.

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Halogenation of Carbonyl and Related Compounds

Larock

Zhang

2018

Comprehensive Organic Transformations

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Aldehydes and Ketones Acetals Lactols Carboxylic Acids Acid Halides Esters and Lactones Amides and Lactams Imides and Related Compounds Nitriles

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Highly Efficient Method for C-5 Halogenation of Pyrimidine-Based Nucleosides in Ionic Liquids

Cited by 8 publications

References 30 publications

BF3@K10: An Efficient Heterogeneous Montmorillonite Catalyst for the Halogenation of N-Heterocycles

BF3@K10: An Efficient Heterogeneous Montmorillonite Catalyst for the Halogenation of N-Heterocycles

Facile Access to Bromonucleosides Using Sodium Monobromoisocyanurate (SMBI)

Halogenation of Carbonyl and Related Compounds

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