2-Aminopurine derivatives with C6-substituted olefin as novel cross-linking agents and the synthesis of the corresponding β-phosphoramidite precursors

Nagatsugi, Fumi; Uemura, K.; Nakashima, S.; Maëda, Minoru; Sasaki, Shigeki

doi:10.1016/s0040-4020(97)00069-0

Cited by 71 publications

(34 citation statements)

References 21 publications

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“…The conjugate addition of a series of secondary and primary amines to 6-ethynylpurines 7 and 8 were performed under analogous conditions as for 6-vinylpurines (Scheme 3, Table 3). Secondary amines reacted slowly but cleanly to give (E)-configured 9-benzylated enamines 9 in high yields (Entries 1-5) and 9-THP-substituted enamines 10 in somewhat lower yields, accompanied by partial cleavage of the THP group (Entries [10][11][12][13][14]. On the other hand, the addition of primary amines gave mixtures of (Z)-and (E)-configured enamines 11 and 12 with the (Z) isomers usually prevailing.…”

Section: Conjugate Addition To 6-ethynylpurinesmentioning

confidence: 99%

“…The very first example was described by Sasaki et al, [12] who used the addition of thiophenol to a 2-amino-6-vinylpurine nucleoside in the synthesis of a 2-amino-6-[2-(phenylsulfanyl)-ethyl]purine nucleoside, which was incorporated into oligonucleotides and used as a precursor for the corresponding 6-vinylpurine, which formed stable cross-links in DNA duplexes by the conjugate addition of cytosine. Czernecki et al [13] reported a radical azidophenylselenylation of vinylpurine in the synthesis of a 6-[2-(acylamino)ethyl]purine nucleoside.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis of Purines Bearing Functionalized C‐Substituents by the Conjugate Addition of Nucleophiles to 6‐Vinylpurines and 6‐Ethynylpurines

et al. 2006

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Purines bearing diverse β‐substituted ethyl or vinyl groups in position 6 were prepared by the conjugate addition of N‐, O‐ and S‐nucleophiles to 6‐vinylpurines or 6‐ethynylpurines. The scope of this methodology was systematically studied. The addition of amines, alcoholates and thiolates to 6‐vinylpurines gave the corresponsing 6‐(2‐aminoethyl)‐, 6‐(2‐alkoxyethyl)‐ and 6‐[2‐(alkylsulfanyl)ethyl]purines. The addition of amines to 6‐ethynylpurines gave 6‐(2‐aminovinyl)purines, while the addition of alcoholates and thiolates gave 6‐(2‐dialkoxyethyl)‐ and 6‐[2‐bis(alkylsulfanyl)ethyl]purines. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

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Section: Conjugate Addition To 6-ethynylpurinesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Synthesis of Purines Bearing Functionalized C‐Substituents by the Conjugate Addition of Nucleophiles to 6‐Vinylpurines and 6‐Ethynylpurines

et al. 2006

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“…In our approach to selective functional oligonucleotides, we have developed a 2-amino-6-vinylpurine (1) as a cytosine selective cross-linking agent within a duplex. 50,51) It is notable that the alkylating activity of 1 can be autogenerated within the duplex from its stable precursor, a phenylsulfide or phenylsulfoxide derivative (Fig. 3).…”

Section: Mutagenesis Using Tfos Bearing 2-amino-6-vinylpurine Derivatmentioning

confidence: 99%

Chemical Tools for Targeted Mutagenesis of DNA Based on Triple Helix Formation

Nagatsugi

Sasaki

2004

Biological & Pharmaceutical Bulletin

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“…For example, DNA duplexes with interstrand cross-linkers, [i],[ii],[iii],[iv],[v],[vi] hydrogen (Watson-Crick) base pair bonding models (Figure 1), [vii],[viii] inhibitors of ribonucleotide reductase [ix] or HIV reverse transcriptase, [x] a model of the mechanism for the repair of DNA photolesion, [xi] supramolecular self-assembly, [xii] as well as protein binding [8] have all been studied with their aid. Some of the interstrand cross-linked oligonucleotides exhibit interesting biological properties such as thrombin inhibition.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and EPR Studies of 2′‐Deoxyuridines with Alkynyl, Rodlike Linkages

Sniady

Sevilla

Meneni

et al. 2009

Chemistry A European J

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Sonogashira coupling of diacetyl 5-ethynyl-2'-deoxyuridine with diacetyl 5-iodo-2'-deoxyuridine gave the acylated ethynediyl-linked 2'-deoxyuridine dimer (3b) (63%) that was deprotected with ammonia/methanol to ethynediyl-linked 2'-deoxyuridines (3a) (79%). Reaction of 5-ethynyl-2'-deoxyuridine (1a) with 5-iodo-2'-deoxyuridine gave the furopyrimidine linked to 2'-deoxyuridine (78%). Catalytic oxidative coupling of 1a (O2, CuI, Pd/C, DMF) gave the butadiynediyl-linked 2'-deoxyuridines (4) (84%). Double Sonogashira coupling of 5-iodo-2'-deoxyuridine with 1,4-bis(ethynyl)benzene gave 1,4-phenylenediethyne-bridged 5-ethynyl-2'-deoxyuridines (5, 83%). Cu-catalyzed cycloisomerization of dimers 4 and 5 gave their furopyrimidine derivatives. One electron addition to 1a, 3a and 4 gave the anion radical whose ESR spectra showed the unpaired electron largely localized at C6 of one uracil ring (17 G doublet) at 77 K. For the ethynediyl- and butadiynyl-linked uridines 3a and 4 the ESR spectra of their one electron oxidized species at 77 K showed that the unpaired electron is delocalized over both rings. Thus structures 3a and 4 provide an efficient electronic link for hole conduction between the uracil rings. However, for the excess electron, an activation barrier prevents coupling to both rings. These dimeric structures could provide a gate that could separate hole transfer from electron transport between strands in DNA systems. In the crystal structure of acylated dimer 3b the bases were found in the anti position to each other across the ethynyl link. Similar anti conformation was preserved in the derived furopyrimidine–deoxyuridine dinucleoside.

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2-Aminopurine derivatives with C6-substituted olefin as novel cross-linking agents and the synthesis of the corresponding β-phosphoramidite precursors

Cited by 71 publications

References 21 publications

Synthesis of Purines Bearing Functionalized C‐Substituents by the Conjugate Addition of Nucleophiles to 6‐Vinylpurines and 6‐Ethynylpurines

Synthesis of Purines Bearing Functionalized C‐Substituents by the Conjugate Addition of Nucleophiles to 6‐Vinylpurines and 6‐Ethynylpurines

Chemical Tools for Targeted Mutagenesis of DNA Based on Triple Helix Formation

Synthesis and EPR Studies of 2′‐Deoxyuridines with Alkynyl, Rodlike Linkages

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