The protecting-group free selective 3′-functionalization of nucleosides

The protecting-group free selective 3'-functionalization of nucleosides.

The direct and chemoselective 3'-phosphoramidation, phosphorylation and acylation of nucleosides are described. Upon the discovery of a novel 3'-phosphorylamidation of therapeutic nucleoside analogues with DBU, we explored the mechanism of this rare selectivity through a combination of NMR spectroscopy and computational studies. The NMR and computational findings allowed us to develop a predict...

Selective functionalization of 3-D polymer microstructures.

We demonstrate the selective functionalization of 3-D polymer microstructures that were created using multiphoton absorption polymerization. By fabricating different portions of the structures with acrylic and methacrylic polymers, we are able to take advantage of the differential reactivities of these materials to perform functionalization chemistry on a single polymeric component. We demonstr...

Strategies toward protecting group-free glycosylation through selective activation of the anomeric center

Glycosylation is an immensely important biological process and one that is highly controlled and very efficient in nature. However, in a chemical laboratory the process is much more challenging and usually requires the extensive use of protecting groups to squelch reactivity at undesired reactive moieties. Nonetheless, by taking advantage of the differential reactivity of the anomeric center, a...

Strategies for Protecting Group Free Glycosidation

Photolabile Protecting Groups for Nucleosides: Mechanistic Studies of the 2-(2-Nitrophenyl)ethyl Group

The photochemistry of several 2-(2-nitrophenyl)ethyl-caged compounds including caged thymidine nucleosides was studied by nanosecond laser flash photolysis and stationary illumination experiments with quantitative HPLC analysis for quantum yields and product distribution. Effects of solvent basicity and acidity were investigated by varying the H2O content and HCl concentration, respectively, in...