Supramolecular systems have shown great potential for controlling photochemical reactions of cinnamate ester derivatives. These olefins undergo one of two topochemical reactions depending on the reaction conditions: when free in solution they undergo cis/trans-isomerization, when constrained within 3.2-4.5 Å they undergo photocyclization to afford truxinate and truxillate cyclobutanes. Here we introduce a new supramolecular strategy utilizing G-quadruplex self-assembly to template [2+2] photocyloadditions of cinnamate ester guanosine derivatives with high yields and stereo-control. To utilize the G-quadruplex as a scaffold for cycloadditions, we have synthesized a new 5'-(ortho-methoxy)cinnamoyl guanosine derivative (G1) and examined its self-assembly and photochemical reactivity. Irradiation of G1, as a free monomer in solution, results in only cis/trans isomerization. Although, when G1 is self-assembled into a G-quadruplex and irradiated [2+2] cycloaddition occurs.

Utilizing the G-quadruplex as a scaffold for [2+2] photocycloadditions of cinnamate esters

254th National Meeting (2017)

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