Stereoselectivities in the Coupling Reaction between Silylated Pyrimidine Bases and 1-Halo-2,3-dideoxyribose

Kawakami, Hiroshi; Ebata, Takashi; Koseki, Koshi; Matsumoto, Katsuya; Matsushita, Hajime; Naoi, Y.; Itoh, Kazuo

doi:10.3987/com-90-5563

Cited by 25 publications

(9 citation statements)

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“…To oxidize LGO‐Cyrene TM , our strategy relied on the well‐established Baeyer–Villiger oxidation. This well‐known reaction usually involves a peracid, such as meta ‐chloroperbenzoic acid ( m ‐CPBA) or peracetic acid, that reacts with a cyclic ketone to form an intermediate that rearranges into a lactone. Several groups have investigated the use of chemoenzymatic conditions to make this process greener and more sustainable.…”

Section: Resultsmentioning

confidence: 99%

“…Recently, we reported the synthesis of renewable acrylate monomers with ( S )‐γ‐hydroxymethyl‐α,β‐butenolide (HBO), a bio‐based molecule derived from LGO, to produce high‐ T g bio‐based polymers with post‐polymerization possibilities (Scheme ) . Over the last decades, several processes that involve either chemical or chemoenzymatic conditions have been proposed to synthesize HBO from LGO by Baeyer–Villiger oxidations. For example, in 2018 we reported the organic‐solvent‐free oxidation of LGO into HBO with 30 % aqueous H 2 O 2 without any catalyst (Scheme ).…”

Section: Introductionmentioning

confidence: 99%

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Sustainable Synthesis and Polycondensation of Levoglucosenone‐Cyrene‐Based Bicyclic Diol Monomer: Access to Renewable Polyesters

et al. 2020

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The already‐reported, low‐yielding, and non‐sustainable Et3N‐mediated homocoupling of levoglucosenone (LGO) into the corresponding LGO‐CyreneTM diketone has been revisited and greened‐up. The use of methanol as both a renewable solvent and catalyst and K2CO3 as a safe inorganic base improved the reaction significantly with regards to yield, purification, and green aspects. LGO‐CyreneTM was then subjected to a one‐pot, H2O2‐mediated Baeyer–Villiger oxidation/rearrangement followed by an acidic hydrolysis to produce a new sterically hindered bicyclic monomer, 2H‐HBO‐HBO. This diol was further polymerized in bulk with diacyl chlorides to access new promising renewable polyesters that exhibit glass transition temperatures (Tg) from −1 to 81 °C and a good thermostability with a temperature at which 50 % of the mass is lost (Td50 %) of 349–406 °C.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Sustainable Synthesis and Polycondensation of Levoglucosenone‐Cyrene‐Based Bicyclic Diol Monomer: Access to Renewable Polyesters

et al. 2020

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“…Indeed, LGO is a chiral synthon that can be used in the synthesis of a wide variety of biologically active compounds such as pharmaceutical ingredients, agrochemicals, polymers, or specialty chemicals (Miftakhov et al, 1994 ; Budarin et al, 2011 ). Among them, ( S )-γ-hydroxymethyl-α,β-butenolide (aka HBO ) is certainly the most interesting since it is a precursor of many drugs (Enders et al, 2002 ), flavors (Kawakami et al, 1990 ), and antiviral agents (Flores et al, 2011 ).…”

Section: Introductionmentioning

confidence: 99%

“…Kawakami (Kawakami et al, 1990 ) and Paris (Paris et al, 2013 ) reported the most efficient methods for HBO synthesis, being obtained high overall yields (ca. 80–90%, Figure 1 ).…”

Section: Introductionmentioning

confidence: 99%

Lipase-Catalyzed Baeyer-Villiger Oxidation of Cellulose-Derived Levoglucosenone into (S)-γ-Hydroxymethyl-α,β-Butenolide: Optimization by Response Surface Methodology

et al. 2016

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Cellulose-derived levoglucosenone (LGO) has been efficiently converted into pure (S)-γ-hydroxymethyl-α,β-butenolide (HBO), a chemical platform suited for the synthesis of drugs, flavors and antiviral agents. This process involves two-steps: a lipase-catalyzed Baeyer-Villiger oxidation of LGO followed by an acid hydrolysis of the reaction mixture to provide pure HBO. Response surface methodology (RSM), based on central composite face-centered (CCF) design, was employed to evaluate the factors effecting the enzyme-catalyzed reaction: pka of solid buffer (7.2–9.6), LGO concentration (0.5–1 M) and enzyme loading (55–285 PLU.mmol-1). Enzyme loading and pka of solid buffer were found to be important factors to the reaction efficiency (as measured by the conversion of LGO) while only the later had significant effects on the enzyme recyclability (as measured by the enzyme residual activity). LGO concentration influences both responses by its interaction with the enzyme loading and pka of solid buffer. The optimal conditions which allow to convert at least 80% of LGO in 2 h at 40°C and reuse the enzyme for a subsequent cycle were found to be: solid buffer pka = 7.5, [LGO] = 0.50 M and 113 PLU.mmol-1 for the lipase. A good agreement between experimental and predicted values was obtained and the model validity confirmed (p < 0.05). Alternative optimal conditions were explored using Monte Carlo simulations for risk analysis, being estimated the experimental region where the LGO conversion higher than 80% is fulfilled at a specific risk of failure.

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“…-UV (MeOH): h,,, (E) = 309 nm (sh 12400), 299 (14000), 224 (38000). Chloro-1 -(2,3-dideox y-5-0-[ (I, 1 -dimethylethyl) dimeth ylsilyll- (15): From the second zone 15 (790 mg, 35%) was isolated as a colorless oil. -TLC (silica gel, CH2C1Jacetone, 9: 1): Rf = 0.52.…”

Section: -Chloro-1-(2'-deoxy-p-d-erythro-pentofuranosyl) -1h-imidazomentioning

confidence: 99%

Imidazo[1,2‐a]pyrimidine 2′‐Deoxyribo‐ and 2′,3′‐Dideoxyribonucleosides: Glycosylation of the Nucleobase Anion

Seela

Gumbiowski

1992

Liebigs Ann. Chem.

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The synthesis of the imidazo[1,2‐a]pyrimidine 2′‐deoxyribonucleosides 2a and 3a related to 2′‐deoxyguanosine or 2′‐deoxyinosine is described. Glycosylation of the nucleobase anion of 5 with 2′‐deoxy‐3,5‐bis‐O‐(4‐methylbenzoyl)‐α‐D‐erythro‐pentofuranosyl chloride (6) yielded stereoselectively the N‐1 β‐D‐deoxyribofuranoside 7. Under the same conditions the 2′,3′‐dideoxyrihalogenoses 11 and 14 were employed to afford anomeric mixtures of glycosylation products (12, 13 and 15, 16). The glycosylation products obtained from the 2′‐deoxyribo‐ and 2′,3′‐dideoxyribo halides were then converted into the final nucleosides (2a, b and 3a, b). The inhibitory activity of the imidazo[1,2‐a]pyrimidine 2′,3′‐dideoxynucleoside 5′‐triphosphates 28a and 28b against HIV reverse transcriptase was tested.

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Stereoselectivities in the Coupling Reaction between Silylated Pyrimidine Bases and 1-Halo-2,3-dideoxyribose

Cited by 25 publications

References 0 publications

Sustainable Synthesis and Polycondensation of Levoglucosenone‐Cyrene‐Based Bicyclic Diol Monomer: Access to Renewable Polyesters

Sustainable Synthesis and Polycondensation of Levoglucosenone‐Cyrene‐Based Bicyclic Diol Monomer: Access to Renewable Polyesters

Lipase-Catalyzed Baeyer-Villiger Oxidation of Cellulose-Derived Levoglucosenone into (S)-γ-Hydroxymethyl-α,β-Butenolide: Optimization by Response Surface Methodology

Imidazo[1,2‐a]pyrimidine 2′‐Deoxyribo‐ and 2′,3′‐Dideoxyribonucleosides: Glycosylation of the Nucleobase Anion

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