Hexamethyldisilazane-Promoted Sonogashira Reaction of Polyfunctionalized N-Containing Heterocycles

Inoûye, Masahiko; Abe, Hajime; Doi, Yasuhiro; Azuchi, Junichi; Shirato, Wataru; Chiba, Junya

doi:10.3987/com-10-s(e)89

Cited by 9 publications

(3 citation statements)

References 11 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This implied that the masking of the amide of 7-deazaguanine with the proper protecting group could be important for this reaction to proceed. Then an alternative cross-coupling condition, which utilized hexamethyldisilazane (HMDS) as both a base and transient 6-carbonyl silylating reagent, was used . In Table , entries 1–4, the equivalent of the base and reaction temperature were assessed, and the target product was obtained in 83% when the reaction was carried out at 40 °C in the presence of 6 equiv of HMDS (entry 4).…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Properties of 2′-OMe-RNAs Modified with Cross-Linkable 7-Deazaguanosine Derivatives

et al. 2018

View full text Add to dashboard Cite

Cross-linkable 7-deaza-6-vinylguanosine (ADVP) and 7-propynyl-7-deaza-6-vinylguanosine (ADpVP) derivatives were synthesized and successfully incorporated into 2'-OMe-RNA oligonucleotides by solid-phase oligonucleotide synthesis. Analysis of their cross-link properties revealed that the 7-propynyl substituent on ADpVP induces a significant enhancement of the cross-link kinetics of the proximal 6-vinyl group to the complementary uracil base in the target RNA compared to that of ADVP. In addition, the 2'-OMe-RNA oligonucleotide containing ADpVP exhibited a higher antisense effect on luciferase production in the cell lysate than that of ADVP. These results suggested that the 7-substituted 7-deaza-6-vinylguanosine derivatives can be used as potent cross-linkers to target mRNA inside of cells.

show abstract

Section: Resultsmentioning

confidence: 99%

Synthesis and Properties of 2′-OMe-RNAs Modified with Cross-Linkable 7-Deazaguanosine Derivatives

et al. 2018

View full text Add to dashboard Cite

show abstract

“…The overall scheme in part B is displayed in Figures 4.62.2 and 4.62.3. Starting from the key compound 9, seven types of alkynyl C-nucleosides were obtained in good yields (67% to 92%) via palladium-catalyzed Sonogashira coupling with halogen-tethered pyrimidine and pyridine derivatives as nonnatural nucleobases (Doi et al, 2008;Inouye et al, 2011;Shirato et al, 2015). Subsequent appropriate protection and conventional phosphoramidation of the C-nucleosides afforded the corresponding nonnatural phosphoramidites in moderate to good yields (53% to 98%).…”

Section: Synthesis Of Alkynyl C-nucleosides and Their Phosphoramiditesmentioning

confidence: 99%

Synthesis of Nonnatural Oligonucleotides Made Exclusively of Alkynyl C‐Nucleosides with Nonnatural Bases

Chiba

Inoûye

2015

CP Nucleic Acid Chemistry

Self Cite

View full text Add to dashboard Cite

This unit describes detailed procedures for the preparation of nonnatural C-nucleosides comprising seven types of nonnatural nucleobases attached to 1'-position of 2'-deoxyribose through an acetylene bond with the β-configuration. In addition, derivatization of these alkynyl C-nucleosides into the corresponding phosphoramidites and the subsequent oligonucleotide synthesis are also presented. The processes are depicted in three parts. The first basic protocol deals with the synthesis of a key intermediate, 5-O-DMTr-protected 1-ethynyl-2-deoxy-β-D-ribofuranoside. The second basic protocol mentions the procedures of the preparation of nonnatural C-nucleosides by a palladium-catalyzed coupling reaction of the ethynyl intermediate and halogen-attached nonnatural nucleobases. The synthetic procedures of the corresponding nonnatural phosporamidites are also described. The third basic protocol presents the solid-phase, automated synthesis of nonnatural oligonucleotides composed exclusively of the nonnatural C-nucleotides.

show abstract

“…Various heterocycles can be introduced into our nucleoside skeleton by means of acetylene chemistry with organometallic strategy. − In this context, further modification of non-natural bases has been carried out in order to imitate natural DNA more closely. Figure displays non-natural base pairs consisting of our previous A analogues, A* (2-aminopyrimidine) and D* (2,4-diaminopyrimidine), with T* (1-methyluracyl) for the T -analogue.…”

mentioning

confidence: 99%

2-Aminopyridine as a Nucleobase Substitute for Adenine in DNA-like Architectures: Synthesis of Alkynyl C-Nucleotides and Their Hybridization Characteristics

et al. 2019

Self Cite

View full text Add to dashboard Cite

Halogenated 2-aminopyridine was attached to the acetylene terminal of ethynyl C-2deoxy-β-D-ribofuranoside as a nucleobase substitute, and then, the C-nucleoside was incorporated into natural DNAs. The resulting chimeric DNA constructed double helical structures with the complementary chimeric DNA. In the duplex, 2-aminopyridine functioned as an adenine analogue that formed a base pair with a non-natural thymine isostere. Artificial homooligomers were also prepared only from the adenine-type C-nucleoside and proven to form completely artificial double helices with the corresponding artificial thymine-type homooligomers.

show abstract

Hexamethyldisilazane-Promoted Sonogashira Reaction of Polyfunctionalized N-Containing Heterocycles

Cited by 9 publications

References 11 publications

Synthesis and Properties of 2′-OMe-RNAs Modified with Cross-Linkable 7-Deazaguanosine Derivatives

Synthesis and Properties of 2′-OMe-RNAs Modified with Cross-Linkable 7-Deazaguanosine Derivatives

Synthesis of Nonnatural Oligonucleotides Made Exclusively of Alkynyl C‐Nucleosides with Nonnatural Bases

2-Aminopyridine as a Nucleobase Substitute for Adenine in DNA-like Architectures: Synthesis of Alkynyl C-Nucleotides and Their Hybridization Characteristics

Contact Info

Product

Resources

About