Efficient Synthesis of Unprotected C-5-Aryl/Heteroaryl-2'-deoxyuridine via a Suzuki-Miyaura Reaction in Aqueous Media

Fresneau, Nathalie; Hiebel, Marie‐Aude; Agrofoglio, Luigi A.; Berteina‐Raboin, Sabine

doi:10.3390/molecules171214409

Cited by 44 publications

(29 citation statements)

References 53 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Compared to related C-C bond formations, the environmentally benign nature, high functional group tolerance, wide commercial availability of the reactants, and compatibility with aqueous conditions are advantageous [10][11][12]. As a result, various research groups have utilized and reviewed this reaction for the derivatization of complex molecules such as natural products [13][14][15][16] and nucleosides [17][18][19][20][21][22][23]. The mechanism of this reaction originally proposed by Miyaura and Suzuki has been revisited recently, which provides insights useful for rational reaction optimization [24][25][26].…”

Section: Introductionmentioning

confidence: 99%

The Suzuki–Miyaura Cross-Coupling as a Versatile Tool for Peptide Diversification and Cyclization

et al. 2017

View full text Add to dashboard Cite

Abstract:The (site-selective) derivatization of amino acids and peptides represents an attractive field with potential applications in the establishment of structure-activity relationships and labeling of bioactive compounds. In this respect, bioorthogonal cross-coupling reactions provide valuable means for ready access to peptide analogues with diversified structure and function. Due to the complex and chiral nature of peptides, mild reaction conditions are preferred; hence, a suitable cross-coupling reaction is required for the chemical modification of these challenging substrates. The Suzuki reaction, involving organoboron species, is appropriate given the stability and environmentally benign nature of these reactants and their amenability to be applied in (partial) aqueous reaction conditions, an expected requirement upon the derivatization of peptides. Concerning the halogenated reaction partner, residues bearing halogen moieties can either be introduced directly as halogenated amino acids during solid-phase peptide synthesis (SPPS) or genetically encoded into larger proteins. A reversed approach building in boron in the peptidic backbone is also possible. Furthermore, based on this complementarity, cyclic peptides can be prepared by halogenation, and borylation of two amino acid side chains present within the same peptidic substrate. Here, the Suzuki-Miyaura reaction is a tool to induce the desired cyclization. In this review, we discuss diverse amino acid and peptide-based applications explored by means of this extremely versatile cross-coupling reaction. With the advent of peptide-based drugs, versatile bioorthogonal conversions on these substrates have become highly valuable.

show abstract

Section: Introductionmentioning

confidence: 99%

The Suzuki–Miyaura Cross-Coupling as a Versatile Tool for Peptide Diversification and Cyclization

et al. 2017

View full text Add to dashboard Cite

show abstract

“…Thus, uracil or uridine containing a halogen atom on C5, usually iodine or bromine, were treated with appropriate organostannanes derived from different heterocycles like furan, thiophene, pyridine in the presence of transition metal complexes producing 5-hetaryl derivatives in satisfactory yields. [43][44][45] Other types of cross-coupling reaction involving an organometallic catalyst applied in the syntheses of 5-hetaryl derivatives have recently been reviewed. 46 The less explored strategy for the synthesis of 5-hetaryl uracil derivatives involves 1,3-dipolar cycloaddition reactions.…”

mentioning

confidence: 99%

Synthesis of 5-hetaryluracil derivatives via 1,3-dipolar cycloaddition reaction

Jakubiec¹,

Przypis²,

Suwiński³

et al. 2016

Arkivoc

View full text Add to dashboard Cite

1,3-Dipolar cycloaddition is a convenient method for construction of various heterocyclic systems. We applied this method for the synthesis 5-hetaryluracil derivatives where substituted uracils played the role of 1,3-dipoles or dipolarophiles. Treatment of the nitrile oxide derived from 5-formyluracil and substituted alkenes gave the appropriate 5-(4,5-dihydroisoxazol-3-yl)pyrimidine-2,4(1H,3H)-diones, which by oxidation with Nbromosuccinimide were transformed into appropriate 5-(isoxazol-3-yl)uracils. When 5-cyanouracil was used as a dipolarophile in the reaction with nitrile oxides, generated from aromatic aldoximes, several 5-(1,2,4-oxadiazol-5-yl)uracils were obtained. An alternative reaction of 5-formyluracil with an excess of nitriles in the presence of cerium ammonium nitrate as an oxidant gave 1,2,4-oxadiazol-3-yl derivatives in moderate yields.

show abstract

“…Arylation of 78a with m-xylene gave a mixture of the three regioisomers (88%) from which the 2,4-dimethylphenyl isomer 91c was isolated in 55% yield (entry 2). 54 However, coupling of 78a with arenes bearing electron withdraw group (EWG) either failed (nitrobenzene) or gave the corresponding 5-arylated products in low yields (1,2 under similar conditions to give 91e but 14 equiv. of TBAF was required (entry 10).…”

Section: Tbaf-promoted Pd-catalyzed Direct Arylation Of 5-halouracilmentioning

confidence: 99%

“…12,30,37,[53][54][55][56][57][58][59][60] The synthesis of numerous 5-substituted pyrimidine nucleosides via Pdassisted routes have been reviewed. 12 …”

Section: Scheme 1 General Scheme For Pd-catalyzed Cross Couplingmentioning

confidence: 99%

“…To continue with the previous funding (Scheme 30 in Chapter 3.1.1.2), the authentic samples of m-79b, o-79b and p-79b were synthesized via Suzuki coupling 54 to elucidate the ratio of the three isomers. By comparing the retention time of each authetic isomer via GC and spiking the reaction mixture with the authentic sample, the ratio of ortho/meta/para was established as 3:2:1.…”

Section: Tbaf-promoted Pd-catalyzed Direct Arylation Of 5-halouracilmentioning

Efficient Synthesis of Unprotected C-5-Aryl/Heteroaryl-2'-deoxyuridine via a Suzuki-Miyaura Reaction in Aqueous Media

Cited by 44 publications

References 53 publications

The Suzuki–Miyaura Cross-Coupling as a Versatile Tool for Peptide Diversification and Cyclization

The Suzuki–Miyaura Cross-Coupling as a Versatile Tool for Peptide Diversification and Cyclization

Synthesis of 5-hetaryluracil derivatives via 1,3-dipolar cycloaddition reaction

Novel Approaches for the Synthesis of C-5 Modified Pyrimidine Nucleosides

Contact Info

Product

Resources

About