Dinucleotides containing two allyl groups by combinations of allyl phosphotriesters, 5-allyl-, 2′-O-allyl- and 2′-arabino-O-allyl uridine derivatives as substrates for ring-closing metathesis

Børsting, Philip; Freitag, Morten; Nielsen, Poul

doi:10.1016/j.tet.2004.09.023

Cited by 28 publications

(13 citation statements)

References 64 publications

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“…Allyl hexyl ether (AHE) and racemic allylisopropylidene glycerol (AIG) were both synthesized from 1-hexanol and isopropylidene glycerol, respectively, by the Williamson reaction using allyl bromide and tetrabutylammonium bromide as the phase transfer catalyst. 35 Allyl ribofuranoside (AR) was prepared by O-glycosidation of D-ribose in allyl alcohol (Scheme 3). 19 AR can be further converted into the cyclic acetal AIR by reacting the two hydroxylic groups in cis-position at carbons C2 and C3 with acetone under acid catalysis.…”

Section: Resultsmentioning

confidence: 99%

Compared Reactivity of Allyl Ribosides in UV-Initiated Free Radical Copolymerization with Acceptor Monomers

et al. 2009

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The free radical copolymerization of allyl ribosides with diethyl fumarate and maleate was investigated for evaluating the potential of donor-acceptor type copolymerization applied to unsaturated monomers derived from renewable feedstock. The photochemically induced polymerization of model monomer blends was conducted in solution as well as in liquid films of bulk reactants. Infrared spectroscopy was used to monitor the consumption of the allylic donor monomer and of the butenedicarboxylate acceptor monomers. The method allowed examining the influence of the nature of the monomer pair and of their relative concentration on the kinetic profiles. Comparison with reference vinyl ether monomers confirmed the expected lower reactivity of the blends containing allylic derivatives. SEC and NMR analysis supported the occurrence of degradative chain transfer during the reactions involving allylic monomers. However, allyl derivatives of glycerol as well as O-allyl ribosides were shown to undergo polymerization with high conversion of both monomers when blended in appropriate molar ratios.

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Section: Resultsmentioning

confidence: 99%

Compared Reactivity of Allyl Ribosides in UV-Initiated Free Radical Copolymerization with Acceptor Monomers

et al. 2009

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“…Similarly bisphosphate gave the trinucleotide with catalyst A in 60% yield. A recent study on dinucleotides revealed that the efficiency of RCM reaction depends upon the substrate structure and the E/Z ratio depends on the configuration of the substrate [86]. The yield and the rate of the reaction also depended on the substrate structure.…”

Section: Synthesis Of Nitrogen Phosphorus and Sulphur Heterocyclesmentioning

confidence: 99%

Synthesis of Macrocyclic Compounds by Ring Closing Metathesis

Majumdar¹,

Rahaman²,

Roy

2007

COC

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Synthesis of macrocyclic compounds including natural products with varying complexities by ring closing metathesis is described. Twelve to very large rings that have been synthesized in moderate to good yields and the synthesis of larger rings as a part of bi-or poly-cyclic systems are also described in this review. The effectiveness of the Grubbs' catalyst towards the RCM in presence of free alcohols, epoxides as well as with various silyl ethers is also presented. In addition to these, the application of RCM towards the syntheses of various naturally occurring macrolides, lactams and unnatural cyclic poly ethers, catenanes etc. are described.

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“…A number of cyclic dinucleotides have been obtained by this general strategy. [20][21][22][23][24][25][26][27][28][29] As the first example, four stereoisomeric dinucleotides with unsaturated 7-membered rings in the internucleoside linkage were obtained from RCM-reactions on substrates with an allyl phosphotriester linkage and an adjacent 5 -C-vinyl group. 20, 21 Also cyclic dinucleotides in which the ring is based on the combination of an allyl phosphotriester and a 5-allyluracil moiety have been efficiently obtained giving 14-membered ring systems.…”

Section: Introductionmentioning

confidence: 99%

“…20, 21 Also cyclic dinucleotides in which the ring is based on the combination of an allyl phosphotriester and a 5-allyluracil moiety have been efficiently obtained giving 14-membered ring systems. 22,23, 25 A trinucleotide with two allyl phosphotriester linkages has been used as an efficient RCM-substrate and a cyclic trinucleotide with a 13-membered ring was obtained albeit as a mixture of 8 stereoisomers. 22 Recently, a series of 2 -C to phosphate connections revealing cyclic dinucleotides with 7-10membered rings have been obtained in medium to high yields.…”

Section: Introductionmentioning

confidence: 99%

“…Two adjacent 5-allyluracil moieties have been combined in a cyclic dinucleotide with a very large 20-membered ring, however in this case in a relatively low yield. 25 In a more promising approach, we investigated dinucleotide substrates on which terminal double bonds are placed on the 4 -C or 5 -C positions. In the preliminary study, 24 a 5 -C-allyl group was found to be significantly more reactive than an 4 -C-vinyl group, and a fully protected cyclic dinucleotide with an unsaturated four-carbon 5 -C-to-5 -C connection was obtained.…”

Section: Introductionmentioning

confidence: 99%

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A cyclic dinucleotide with a four-carbon 5′-C-to-5′-C connection; synthesis by RCM, NMR-examination and incorporation into secondary nucleic acid structures

et al. 2006

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A 5'-C-allylthymidine derivative was prepared from thymidine by the application of a stereoselective allylation procedure and its 5'(S)-configuration was confirmed. From this nucleoside derivative, appropriately protected building blocks were prepared and coupled using standard phosphoramidite chemistry to afford a dinucleotide with two 5'-C-allylgroups. This molecule was used as a substrate for a ring-closing metathesis (RCM) reaction and after deprotection, a 1 : 1 mixture of E- and Z-isomers of a cyclic dinucleotide with an unsaturated 5'-C-to-5'-C connection was obtained. Alternatively, a hydrogenation of the double bond and deprotection afforded a saturated cyclic dinucleotide. An advanced NMR-examination confirmed the constitution of this molecule and indicated a restriction in its overall conformational freedom. After variation of the protecting group strategy, a phosphoramidite building block of the saturated cyclic dinucleotide with the 5'-O-position protected as a pixyl ether and the phosphate protected as a methyl phosphotriester was obtained. This building block was used in the preparation of two 14-mer oligonucleotides with a central artificial bend due to the cyclic dinucleotide moiety. These were found to destabilise duplexes, slightly destabilise bulged duplexes but, to some extent, stabilise a three-way junction in high Mg(2+)-concentrations.

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Dinucleotides containing two allyl groups by combinations of allyl phosphotriesters, 5-allyl-, 2′-O-allyl- and 2′-arabino-O-allyl uridine derivatives as substrates for ring-closing metathesis

Cited by 28 publications

References 64 publications

Compared Reactivity of Allyl Ribosides in UV-Initiated Free Radical Copolymerization with Acceptor Monomers

Compared Reactivity of Allyl Ribosides in UV-Initiated Free Radical Copolymerization with Acceptor Monomers

Synthesis of Macrocyclic Compounds by Ring Closing Metathesis

A cyclic dinucleotide with a four-carbon 5′-C-to-5′-C connection; synthesis by RCM, NMR-examination and incorporation into secondary nucleic acid structures

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