70184-00-8Relevant articles and documents
Customizable and Regioselective One-Pot N?H Functionalization of DNA Nucleobases to Create a Library of Nucleobase Derivatives for Biomedical Applications
Borges, Jo?o,Machado, Carmen M.,Mano, Jo?o F.,Rocha, Djenisa H. A.,Silva, Artur M. S.,Silva, Vera L. M.,Sousa, Cristiana F. V.,Sousa, Vera
, p. 4423 - 4433 (2021/08/30)
DNA is one of the most exciting biomolecules in nature for developing supramolecular biofunctional nanoarchitectures owing to the highly specific and selective interactions between complementary Watson-Crick base pairing. Herein, simple and one-pot synthetic procedures have been implemented for producing a library of DNA nucleobase derivatives endowed with reactive functional groups for bioconjugation and cross-linking strategies with other (bio)molecules. Purine and pyrimidine molecules have been regioselectively N?H functionalized either via N-alkylation, N-allylation, N-propargylation or Michael-type reactions and structurally characterized. The influence of the reaction conditions was assessed and discussed. The in vitro biocompatibility of the native and nucleobase derivatives was evaluated by culturing them with human fibroblasts, revealing their cytocompatibility. The library of nucleobase derivatives holds great promise for being coupled to different biomolecules, including biopolymeric materials, lipids, and peptides, thus potentially leading to modular supramolecular nanobiomaterials for biomedicine.
Biomimetic polyorganosiloxanes: Model compounds for new materials
Kociok-Koehn, Gabriele,Mahon, Mary F.,Molloy, Kieran C.,Price, Gareth J.,Prior, Timothy J.,Smith, Douglas R. G.
, p. 7734 - 7746 (2014/05/20)
The chemistry of N-organosilylalkyl-substituted heterocyclic bases (thymine, adenine and cytosine) is described, covering the structures of model compounds, the synthesis of substituted oligo-siloxanes and a preliminary report of the synthesis of a poly(organosiloxane) with pendant N-alkyl(heterocycle) functionalities. N-Alkenylthymines CH2CH(CH2)nT (T = thymine, n = 1 (1), 2 (2), 3 (3)) have been prepared and 2 hydrosilylated to form PhMe2Si(CH2)4T (5). Alternatively, 5 was prepared by reaction of PhMe2Si(CH2)4Br (6) with (O,O-SiMe3)2T, a method which has also been used to prepare PhMe2Si(CH2)4A (7) and PhMe 2Si(CH2)4C (8) (A = adenine, C = cytosine). Model di- and tri-siloxanes [Br(CH2)4(Me) 2Si]2O (10), Me3SiOSi(Me)2(CH 2)4Br (11), PhMe2SiOSi(Me)2(CH 2)4Br (12) and (Me3SiO)2(Me) Si(CH2)4Br (13) have been prepared by hydrosilylation of H2CC(H)(CH2)4Br with an appropriate hydrosiloxane and used to prepare Me3SiO(Me)2Si(CH 2)4T (14), Me3SiO(Me)2Si(CH 2)4A (15) (both from 11), and (Me3SiO) 2(Me)Si(CH2)4T (16), (Me3SiO) 2(Me)Si(CH2)4A (17) (both from 13). 10 reacts with thymine to give a mixture of the pyrimidocyclophane cyclo-T-N,N-[(CH 2)4(Me)2Si]2O (19) and [T(CH 2)4Si(Me)2]2O (20), while cytosine reacts similarly to form cyclo-C-N,N-[(CH2)4(Me) 2Si]2O (21; as an imine) and [C(CH2) 4Si(Me)2]2O (22); adenine only generates [A(CH2)4Si(Me)2]2O (18) in an analogous synthesis. Using a related protocol, polymeric {[MeSi(O)(CH 2)4Br]2[Me2SiO]98} n (23) has been converted to {[MeSi(O)(CH2) 4T]2[Me2SiO]98}n (24) and {[MeSi(O)(CH2)4A]2[Me2SiO] 98}n (25). The structures of 4, 5, 8, 19 and 21, along with a 2:1 adduct of 5 with Ni(dithiobiuret)2 (9) are reported. This journal is the Partner Organisations 2014.
Microwave-assisted N-allylation of uracil and thymine pyrimidine bases
Sacarescu,Atudosie,Simionescu,Sacarescu,Harabagiu
experimental part, p. 602 - 606 (2012/01/13)
This work presents a new synthetic approach to N(1)-allylation of pyrimidine nucleobases with allyl bromide. The increased efficiency of the proposed method is based on two specific elements: (a) the nucleoside N-deprotonation is carried out in a homogeneous system by using sodium methylsulfinyl- methylide in DMSO; (b) the allylation reaction is microwave-assisted. This method ensures high yields (87-88%) of the monoallylated products and short reaction time (1.5 h as compared to tens of hours for classical methods), and provides protection against side reactions. NMR analysis of the crude reaction mixture indicated a ratio of 6-8 : 1 between N(1)-allyl derivatives and N(1),N(3)-diallyl derivatives.
