Stereodefined dinucleoside (3′,5′)-propionamidophosphonates and β-cyanoethylphosphonates and their incorporation into modified oligonucleotides

Woźniak, Lucyna A.; Bukowiecka‐Matusiak, Małgorzata; Burzynska-Pedziwatr, Izabela; Stec, Wojciech J.

doi:10.1016/j.tetlet.2009.01.153

Cited by 10 publications

(8 citation statements)

References 25 publications

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“…Carboxylic acids can be also used as an acylating agents for α-hydroxy phosphonates supported by coupling reagents e.g., N , N ′-dicyclohexylcarbodiimide and 4-dimethylaminopyridineas as the base [ 31 ]. Apart from Michaelis–Arbuzov and Michaelis–Becker reactions, the phosphorus–carbon bond is formed using phospha-Michael addition under basic conditions [ 32 , 33 , 34 , 35 , 36 , 37 ]. Therefore, the possibility of using this approach in the synthesis of bioactive α-acyloxy phosphonates should be considered.…”

Section: Resultsmentioning

confidence: 99%

Promiscuous Lipase-Catalyzed Markovnikov Addition of H-Phosphites to Vinyl Esters for the Synthesis of Cytotoxic α-Acyloxy Phosphonate Derivatives

et al. 2022

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An enzymatic route for phosphorous-carbon- bond formation is developed by discovering new promiscuous activity of lipase. This biocatalytic transformation of phosphorous-carbon- bond addition leads to biologically and pharmacologically relevant α-acyloxy phosphonates with methyl group in α-position. A series of target compounds were synthesized with yields ranging from 54% to 83% by enzymatic reaction with Candida cylindracea (CcL) lipase via Markovnikov addition of H-phosphites to vinyl esters. We carefully analyzed the best conditions for the given reaction such as the type of enzyme, temperature, and type of solvent. The developed protocol is applicable to a range of H-phosphites and vinyl esters significantly simplifying the preparation of synthetically challenging α-pivaloyloxy phosphonates. Further, the obtained compounds were validated as new potential antimicrobial drugs with characteristic E. coli bacterial strains and DNA modification recognized by the Fpg protein, N-methyl purine glycosylases as new substrates. The impact of the methyl group located in the α-position of the studied α-acyloxy phosphonates on the antimicrobial activity was demonstrated. The pivotal role of this group on inhibitory activity against selected pathogenic E. coli strains was revealed. The observed results are especially important in the case of the increasing resistance of bacteria to various drugs and antibiotics.

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Section: Resultsmentioning

confidence: 99%

Promiscuous Lipase-Catalyzed Markovnikov Addition of H-Phosphites to Vinyl Esters for the Synthesis of Cytotoxic α-Acyloxy Phosphonate Derivatives

et al. 2022

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“…In this case the reaction was successfully promoted when new catalytic system containing KOH supported on Al 2 O 3 was used. 13 In another example, dimethyl thiophosphonate was added readily to acrylonitrile or tert-butylacrylate at room temperature without any catalyst, 14 but the reaction of 2-chloroacrylonitrile with dialkyl phosphonates occurred exclusively under catalytic conditions. 15 So, it is clear that the signicant efforts of chemical community are directed toward the development of efficient green methodology, in particular, where the reactions proceed under the action of a low amount of catalyst (recyclable and reusable catalysts are preferred) and in non-toxic solvents (or without using any solvent at all).…”

Section: Introductionmentioning

confidence: 99%

Recent advances in Michael addition of H-phosphonates

Rulev

2014

RSC Adv.

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“…Recently, Tian and co-workers have developed an efficient alternative way to Henry reaction involving a deprotonation of a nitroalkane with the zwitterionic ester enolate to form a nitronate and a subsequent reaction with aldehyde. 4 The conjugate addition of a dialkylphosphonate anion to electron-deficient olefins provided an efficient way to alkylsubstituted phosphonates; 5,6 however, the method required usually a strong base 6a,b,d-h or somewhat drastic conditions. Thus, an alternative way has been used more widely involving the use of trialkyl phosphite.…”

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An Efficient Conjugate Addition of Dialkyl Phosphite to Electron-Deficient Olefins: The Use of a Nucleophilic Organocatalyst to Form a Strong Base

Kim¹,

Kim²,

Kim³

et al. 2013

Bulletin of the Korean Chemical Society

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The formation of a zwitterionic species between electrondeficient olefins and tertiary amine or phosphine is a pivotal and the starting point for the Morita-Baylis-Hillman (MBH) reaction 1 and Rauhut-Currier (RC) reaction. 2 A subsequent 1,2-addition of the zwitterion I, which was generated from methyl acrylate as an example, to aldehyde and a proton movement furnished the Morita-Baylis-Hillman adduct, whereas a conjugate addition to electron-deficient olefins is the Rauhut-Currier reaction, as shown in Scheme 1. Basically, the zwitterion is an ester enolate and could act as a base. 3,4In this respect, White and Baizer reported a phosphinecatalyzed conjugate addition of 2-nitropropane to various electron-deficient olefins, as also shown in Scheme 1.3a Toste and co-workers reported a phosphine-catalyzed conjugate addition of alcohol or water to electron-deficient olefins. Later, Pedduri and Williamson have applied the concept to make tetrahydrofurans.3c Vallribera and co-workers also reported the conjugate addition of β-dicarbonyl compounds to electron-deficient olefins.3d The mechanism of the conjugate additions likely involves the zwitterion I behaving as a base to deprotonate the nitroalkane, alcohol, water and β-dicarbonyl; the nitronate, alkoxide, hydroxide or the enolate of β-dicarbonyl then undergoes the following conjugate additions to electron-deficient olefins. Recently, Tian and co-workers have developed an efficient alternative way to Henry reaction involving a deprotonation of a nitroalkane with the zwitterionic ester enolate to form a nitronate and a subsequent reaction with aldehyde. 4The conjugate addition of a dialkylphosphonate anion to electron-deficient olefins provided an efficient way to alkylsubstituted phosphonates;5,6 however, the method required usually a strong base 6a,b,d-h or somewhat drastic conditions. Thus, an alternative way has been used more widely involving the use of trialkyl phosphite. 7 The reaction between electron-deficient olefins such as methyl acrylate and trialkyl phosphite generated a zwitterionic species at elevated temperature. A subsequent Michaelis-Arbuzov type rearrangement in the presence of phenol afforded the desired alkyl phosphonate, as shown in Scheme 2. In these respects, we presumed that the conjugate addition reactions catalyzed by a nucleophilic organocatalyst such as tributylphosphine could be applied for the synthesis of alkyl phosphonate, as also shown in Scheme 2.At the outset of our experiment we examined the reaction of methyl acrylate and diethyl phosphite in the presence of various nucleophilic catalyst including DABCO, n-Bu 3 P and PPh 3 in CH 3 CN. The use of DABCO (10 mol %, rt, 6 days) did not produce 2a in any trace amount.3b The use of n-Bu 3 P (20 mol %, rt, 2 h) produced 2a in good yield (72%), whereas the reaction in the presence of PPh 3 (20 mol %, reflux, 24 h) produced 2a in a trace amount (< 5%).3b Further studies revealed that the use of 5-10 mol % of n-Bu 3 P showed cleaner reaction and increased the yield of 2a.The reaction mecha...

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Stereodefined dinucleoside (3′,5′)-propionamidophosphonates and β-cyanoethylphosphonates and their incorporation into modified oligonucleotides

Cited by 10 publications

References 25 publications

Promiscuous Lipase-Catalyzed Markovnikov Addition of H-Phosphites to Vinyl Esters for the Synthesis of Cytotoxic α-Acyloxy Phosphonate Derivatives

Promiscuous Lipase-Catalyzed Markovnikov Addition of H-Phosphites to Vinyl Esters for the Synthesis of Cytotoxic α-Acyloxy Phosphonate Derivatives

Recent advances in Michael addition of H-phosphonates

An Efficient Conjugate Addition of Dialkyl Phosphite to Electron-Deficient Olefins: The Use of a Nucleophilic Organocatalyst to Form a Strong Base

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