A Conformationally Locked AminomethylC‐Glycoside and Studies on ItsN‐Pyren‐1‐ylcarbonyl Derivative Inserted into Oligodeoxynucleotides

Abstract

A new conformationally locked aminomethyl C-glycoside has been synthesized and incorporated into oligonucleotides (ONs). The applicability of the monomer in post-ON synthesis (i.e., conjugation by organic synthesis performed on ONs attached to resin) has been successfully demonstrated by condensation with pyren-1-ylcarboxylic acid. The abilities of the pyrenyl-derivatized ONs to recognize abasic sites in complementary strands were investigated by thermal denatur-

C2′-Pyrene-Functionalized Triazole-Linked DNA: Universal DNA/RNA Hybridization Probes

“…18,35,52–54 Full restoration of duplex thermostability, however, is rarely observed. These observations indicate that the pyrene and/or triazole moieties of monomers W - Z intercalate into the duplex core and thereby disrupt interactions between mismatched base pairs, leading to a lack of thermal preference for a particular nucleotide opposite of the modification site.…”

Pyrene-functionalized oligonucleotides and locked nucleic acids (LNAs): Tools for fundamental research, diagnostics, and nanotechnology

“…4). 63 Interestingly, the affinity-enhancing effect of the LNA skeletons is fully compromised as evidenced by the extensive destabilization of singly modified DNA duplexes (Δ T m down to −11 °C). These probes display similar universal base behavior as the structurally simpler monomer 1 (Fig.…”

“…Arrows indicate −1 zipper orientation. 63 Middle : molecular modelling structure of duplex with three −1 interstrand arrangements of monomer 36 ( T m = 77 °C). (Adapted from ref.…”

Acyl Glycosides through Stereospecific Glycosyl Cross-Coupling: Rapid Access to C(sp3)-Linked Glycomimetics

“…12,15,17 The difluorinated surrogate of ganglioside GM4 ( 4 ) demonstrated inhibitory activity of lymphocyte proliferation similar to the natural GM4. 12,15 Jiménez-Barbero 92 and Vogel 96 performed a series of NMR and computational studies on a CF 2 -linked d -galactoside and concluded that the conformational preferences of these unnatural saccharides mimic the natural counterparts, but subtle conformational differences have to be incorporated into the analysis to fully recapitulate the solution structures. 96 These are reminiscent of earlier work by Kishi who systematically investigated the conformational behavior of CH 2 -linked glycosides and demonstrated in a series of papers that CH 2 -linked disaccharides display conformational preferences comparable with natural O -glycosides.…”

“…12,15 Jiménez-Barbero 92 and Vogel 96 performed a series of NMR and computational studies on a CF 2 -linked d -galactoside and concluded that the conformational preferences of these unnatural saccharides mimic the natural counterparts, but subtle conformational differences have to be incorporated into the analysis to fully recapitulate the solution structures. 96 These are reminiscent of earlier work by Kishi who systematically investigated the conformational behavior of CH 2 -linked glycosides and demonstrated in a series of papers that CH 2 -linked disaccharides display conformational preferences comparable with natural O -glycosides. 66−78 Having access to both anomers of acyl glycosides, we next wondered if these compounds could serve as substrates for the preparation of fluorinated glycomimetics.…”