Atom Transfer Polymerization:  Use of Uridine and Adenosine Derivatized Monomers and Initiators

Abstract

The multifunctional monomers 5‘-methacryloyluridine and 5‘-methacryloyladenosine have been polymerized under atom transfer polymerization conditions, giving products of narrow polydispersities as consistent with living polymerization. Initiators derived from both uridine and adenosine have also been used to terminally functionalize poly(methyl methacrylate) and poly(styrene). Both hydroxyl-protected and unprotected initiators successfully gave polymers of predictable and narrow PDI. Atom transfer polymerization of methyl methacrylate with the protected 5‘-bromoisobutyroyluridine initiator 2 with NMPI ligand in conjunction with copper(I) bromide gives polymer with an M n of 13 100 with a very narrow PDI of 1.06 (M n of 11 000 1H NMR). The initiator efficiency is less than unity (e.g., 0.81 for the above reaction), similar to that observed with nonfunctional initiators. 1H NMR is used to demonstrate the presence of the initiator in the polymer. The results demonstrate that this living polymerization system is inert to a multitude of functionality in the initiator, including secondary hydroxyl, silyl ether, tertiary amine, primary amine, secondary amide, etc. Atom transfer polymerization has been used to synthesize well-defined poly(nucleoside)-based polymers which have tremendous potential for templating and polymers used in applications that require biorecognition.

Water soluble triblock and pentablock poly(methacryloyl nucleosides) from copper-mediated living radical polymerisation using PEG macroinitiators

“…All solvents purchased were of the highest grade available from BDH and were used as supplied. Protected (1) and unprotected (2) methacryloyl uridine and protected (3) and unprotected (4) methacryloyl adenosine were synthesised according to literature procedures [34].…”

“…1) and methacryloyl adenosine (3 and 4) has been described previously [34]. PEG macroinitiators (5 and 6, Scheme 1) were synthesised using a modified published procedure [22].…”

“…1) in solution [34], and on a solid support [35]. Recently, there has been renewed interest in these types of polymers in order to use H-bonding to give sequence (and potentially stereo) control, single chain manipulation and controlled polymer folding using different controlled polymerization techniques [36], such as reversible addition-fragmentation chain transfer (RAFT) polymerization [37], nitroxidemediated polymerization [38] and ATRP [39][40][41].…”

Synthesis and assembly behavior of nucleobase‐functionalized block copolymers

“…In addition, Rowan and coworkers [11][12][13] prepared thermoresponsive supramolecular polymer materials, in which the noncovalent interactions are based on single nucleobase moieties. Recent advances in controlled (radical) polymerization techniques such as atom transfer radical polymerization (ATRP) [14][15][16][17][18][19] have further increased activity in the polymer chemistry field. These methods allow the formation of well-defined polymer architectures in which a large variety of biological functionalities, such as nucleobases, can be included.…”

Synthesis and 15N NMR characterization of 4‐vinylbenzyl substituted bases of nucleic acids

“…On the other hand, synthetic polymers are usually much less defined from the standpoint of both the control over molecular mass distribution and the polymerization degree. In earlier work [2,3], some monomers for radical template polymerization were prepared on the basis of esters of methacrylic and acrylic acids corresponding to uracil or adenine derivatives, and these were used for preparation of complementary polymers.…”