Biomimetic polyorganosiloxanes: model compounds for new materials

• Published in: Dalton transactions : an international journal of inorganic chemistry 2014-06, Vol.43 (21), p.7734-7746
• Main Authors: Kociok-Köhn, Gabriele, Mahon, Mary F, Molloy, Kieran C, Price, Gareth J, Prior, Timothy J, Smith, Douglas R G
• Format: Article
• Language: English
• Subjects: Adenine - chemical synthesis; Adenine - chemistry; Adenines; Biomimetic materials; Biomimetic Materials - chemical synthesis; Biomimetic Materials - chemistry; Biomimetics - methods; Cytosine - chemical synthesis; Cytosine - chemistry; Hydrosilylation; Imines; Jewelry; Mathematical models; Models, Molecular; Siloxanes - chemical synthesis; Siloxanes - chemistry; Synthesis; Thymine; Thymine - chemical synthesis; Thymine - chemistry
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/c4dt00554f

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 CH2=CH(CH2)(n)T (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 PhMe2Si(CH2)4C (8) (A = adenine, C = cytosine). Model di- and tri-siloxanes [Br(CH2)4(Me)2Si]2O (10), Me3SiOSi(Me)2(CH2)4Br (11), PhMe2SiOSi(Me)2(CH2)4Br (12) and (Me3SiO)2(Me)Si(CH2)4Br (13) have been prepared by hydrosilylation of H2C[double bond, length as m-dash]C(H)(CH2)4Br with an appropriate hydrosiloxane and used to prepare Me3SiO(Me)2Si(CH2)4T (14), Me3SiO(Me)2Si(CH2)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-[(CH2)4(Me)2Si]2O (19) and [T(CH2)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)(CH2)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.