Modular Synthesis of Substituted []Helicenes ( = 5-7) Starting from Arylmethyl Sulfone and Arylene Dialdehyde: Aldol-Type Condensation, Photocyclization, and Desulfonylative Arylation.

Bis(-methoxyphenysulfonyl)-substituted helicenes were successfully synthesized via UV light irradiation of the corresponding ()-bis(2-aryl-2-(-methoxyphenysulfonyl)ethenyl)arylenes, which were prepared through aldol-type condensation of arylene dialdehydes with arylmethyl -methoxypheny sulfones. By varying the combination of dialdehydes and arylmethyl -methoxypheny sulfones, a series of helicene homologues, ranging from [5] to [7]helicenes, were obtained. The -methoxyphenysulfonyl groups in these helicenes were efficiently replaced with Grignard reagents via Ni-catalyzed Kumada-Tamao-Corriu coupling, yielding the corresponding alkyl- and aryl-substituted derivatives. These dialkyl- and diaryl-substituted helicenes were further expanded into larger π-conjugated systems. The trimethylsilylmethyl-substituted derivative underwent sequential bromination, phosphonation, and a Wittig-Horner reaction with arylaldehydes, affording olefinic helicenes. Furthermore, FeCl-promoted oxidative annulation of the biphenyl-1-yl-substituted derivative resulted in the formation of a "two-blade propeller" closed [6]helicene, fused with dibenzo[]chrysene arrays.