Fullerene lipids: Synthesis of novel nitrogen‐bridged [60]fullerene fatty ester derivatives

Jie, Marcel S. F. Lie Ken; Cheung, Siu Wun; Ho, Janette C. M.

doi:10.1007/s11745-001-0738-0

Cited by 7 publications

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“…Although this chemistry has been developed to prepare a series of nitrogen-bridged C 60 cycloadducts, only a few of them are designed as biological materials. [18][19][20][21] Despite this array of encouraging work, however, no water-soluble fullerene-nucleoside analogues has heretofore been reported. Thus, it was of interest to synthesize nitrogenbridged C 60 -3¢-deoxythimidine adducts, which should open a new frontier to nucleoside analogue chemistry for biological applications.…”

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Synthesis and Characterization of Nitrogen-Bridged [C₆₀]Fullerene/3′-Deoxythimidine Conjugates

Ungurenasu¹,

Pinteala²,

Simionescu³

2005

Synthesis

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3¢-Deoxy-3¢-(1,2,3-triazolfulleryl)thymidine and 3¢-deoxy-3¢- ([5,6]azafulleryl)thymidine were synthesized by the addition of 3¢-azido-3¢-deoxythymidine (AZT) to C 60 .The synthesis and biological proprieties of water-soluble C 60 derivatives have been an area of intensive investigation over the past decade. Functionalization by [3+2] cycloaddition reactions represents the most used strategy to prepare stable cycloadducts with biological activity. [1][2][3][4][5] Starting with the work of Bingel 6 in the [2+3] cycloaddition of a stabilized a-halocarbanion to the C 60 core, attachment of substrates to give water-soluble methanofullerenes has enabled chemists to prepare products with promising preliminary biological activities, such HIVprotease inhibition, 7-10 neuroprotection and apoptosis, 1-13 and DNA photocleavage. 14 Fulleropyrrolines with different biological active substituents on nitrogen have been prepared by cycloaddition of azomethine ylides to fullerene. 15,16 Other versatile but much less investigated for biological applications are the nitrogen-bridged adducts of fullerene. Prato et al. 17 first reported the [2+3] cycloaddition of organic azides to C 60 to yield azafulleroids. Although this chemistry has been developed to prepare a series of nitrogen-bridged C 60 cycloadducts, only a few of them are designed as biological materials. 18-21 Despite this array of encouraging work, however, no water-soluble fullerene-nucleoside analogues has heretofore been reported. Thus, it was of interest to synthesize nitrogenbridged C 60 -3¢-deoxythimidine adducts, which should open a new frontier to nucleoside analogue chemistry for biological applications. In this paper, we report our preliminary results on the reaction of C 60 with 3¢-azido-3¢-deoxythymidine (AZT), the well-known anti-HIV agent.Treatment of a solution of C 60 with AZT in 1,2-dichlorobenzene (ODCB) at 30°C gave the 3¢-deoxy-3¢-(1,2,3-triazolfulleryl)thymidine (1) in 44% yield after purification by column chromatography. Photolysis of 1 in toluene (0.84 × 10 -4 M, l max = 300 nm) yielded the aziridinofullerene derivative 3. Thermally induced conversion of 1 predominantly afforded opened 5,6-addition type azafulleroid 2 beside C 60 . When a mixture of C 60 and AZT was heated in ODCB at 120°C, 2 was obtained as the major product (50%) (Scheme 1). Compounds 1-3 are readily soluble in DMSO, THF, toluene and ODCB. They are also soluble in water [3 mg/mL (1), 2.5 mg/mL (2)]. The solubility in water was checked by adding a solution of products 1-3 in DMSO or THF to water (1:10). The structures of the products 1-3 were determined by elemental and spectroscopic analyses. Scheme 1The TOF MS spectra show the parent ion peaks at m/z = 987.860 (1), 959.847 (2), and 959.848 (3), which agree with the theoretically predicted patterns of isotopic distribution. The 1 H NMR spectra confirmed the thymidine backbone structures of the compounds 1 and 2 for the Downloaded by: University of Queensland. Copyrighted material.

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Synthesis and Characterization of Nitrogen-Bridged [C₆₀]Fullerene/3′-Deoxythimidine Conjugates

Ungurenasu¹,

Pinteala²,

Simionescu³

2005

Synthesis

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“…The yield of the product obtained in the last step of the reaction sequence, i.e., between the corresponding key azido-containing triacylglycerols with [60]fullerene, was rather low (15-18%) when the calculation was based on the amount of [60]fullerene employed. However, in fullerene chemistry the yield of fullerenoid derivatives is normally calculated on the net amount of [60]fullerene consumed during the reaction (19). Based on the net amount of [60]fullerene reacted, the yields of the final reactions described in Schemes 1 and 2 ranged from 45 to 62% and are considered to be reasonable and good.…”

Section: Discussionmentioning

confidence: 99%

Fullerenoid lipids: First synthesis of structured triacylglycerols containing an aza‐[60]fullerence unit

Jie

Cheung

2001

Lipids

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Some 1,2- and 1,3-diacyl glycerols (with acyl groups as stearyl, oleyl, linoleyl, or stearolyl) were synthesized by conventional methods. The diacyl glycerols were esterified with 6-bromo-hexanoic acid to give the corresponding bromo-triacylglycerols (of the type AAB and ABA containing a bromo group at the distal part of the hexanoate chain). The bromo function was transformed to an azide group by reaction of the bromo-triacylglycerols with sodium azide. The resulting azido-triacylglycerols were then reacted with [60]fullerene to give the requisite aza-fullerenoid triacylglycerol of the type ABA or AAB (45-62% yield based on the amount of [60]fullerene reacted). The nitrogen atom attached to the carbon cage formed a "[5,6]open" type aza substructure, which was confirmed by the appearance of 31-32 signals in the region of deltaC 133-148 (carbon shifts of Sp2 carbons of the cage) in the 13C nuclear magnetic resonance spectra. The spectroscopic and mass spectrometric properties of these novel fullerenoid triacylglycerols are reported.

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“…Our research group has recently reported the synthesis of dialkyl 1,2-[6,6]-methano-[60]fullerene dicarboxylate (1) [15] and nitrogen-bridged aza-[60]fullerene fatty ester derivatives (2) [16] (Fig. 4).…”

Section: Exotic Synthetic Lipid Molecules Containing a [60]fullerene mentioning

confidence: 99%

Fullerene lipids: Synthesis of novel nitrogen‐bridged [60]fullerene fatty ester derivatives

Cited by 7 publications

References 24 publications

Synthesis and Characterization of Nitrogen-Bridged [C₆₀]Fullerene/3′-Deoxythimidine Conjugates

Synthesis and Characterization of Nitrogen-Bridged [C₆₀]Fullerene/3′-Deoxythimidine Conjugates

Fullerenoid lipids: First synthesis of structured triacylglycerols containing an aza‐[60]fullerence unit

H. P. Kaufmann Memorial Lecture 2001: Into the Fourth Dimension of Fat Research — Imagination and Inspiration

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Fullerene lipids: Synthesis of novel nitrogen‐bridged [60]fullerene fatty ester derivatives

Cited by 7 publications

References 24 publications

Synthesis and Characterization of Nitrogen-Bridged [C60]Fullerene/3′-Deoxythimidine Conjugates

Synthesis and Characterization of Nitrogen-Bridged [C60]Fullerene/3′-Deoxythimidine Conjugates

Fullerenoid lipids: First synthesis of structured triacylglycerols containing an aza‐[60]fullerence unit

H. P. Kaufmann Memorial Lecture 2001: Into the Fourth Dimension of Fat Research — Imagination and Inspiration

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Synthesis and Characterization of Nitrogen-Bridged [C₆₀]Fullerene/3′-Deoxythimidine Conjugates

Synthesis and Characterization of Nitrogen-Bridged [C₆₀]Fullerene/3′-Deoxythimidine Conjugates