Expanded [2,1][n]Carbohelicenes with 15- and 17-Benzene Rings



Expanded carbohelicenes with structures fused to 15- and 17-benzene were successfully synthesized. Establishing a new synthetic strategy is crucial to realize the development of longer expanded [2,1][n]helicenes with a kekulene-like projection drawing structure. This article describes the sequential integration of the π-elongating Wittig reaction of functionalized phenanthrene units and ring-fusing Yamamoto coupling for the synthesis of [2,1][15] helicenes and [2,1][17] helicenes. X-ray crystallographic structures, photophysical properties, and density functional theory (DFT) calculations revealed the unique characteristics of the synthesized expanded helicenes. Furthermore, because of the high racemization barrier derived from a wide-range intra-helix π–π interaction, the optical resolution of [2,1][17] heli-cene was successfully achieved, and chiroptical properties such as circular dichroism and circularly polarized luminescence were elucidated for the first time as enantiomers of pristine [2,1][n]helicene core.


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