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| 基本情報 |
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| 氏名 |
赤司 治夫 |
| 氏名（カナ） |
ｱｶｼ ﾊﾙｵ |
| 氏名（英語） |
Akashi Haruo |
| 所属 |
機構 研究社会連携機構 ﾌﾛﾝﾃｨｱ理工学研 |
| 職名 |
教授 |
| researchmap研究者コード |
1000113819 |
| researchmap機関 |
岡山理科大学 |
Modular Synthesis of Substituted [n]Helicenes (n = 5–7) Starting from Arylmethyl Sulfone and Arylene Dialdehyde: Aldol-Type Condensation, Photocyclization, and Desulfonylative Arylation
Hikaru Watanabe, Toshiki Sakami, Akira Iwakura, Yuga Nakashima, Moeno Nishinaka, Hiroki Morimoto, Shino Nakashima, Yasuhiro Okuda, Tetsuo Iwanaga, Haruo Akashi, Akihiro Orita
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Bis(p-methoxyphenysulfonyl)-substituted helicenes were successfully synthesized via UV light irradiation of the corresponding (E,E)-bis(2-aryl-2-(p-methoxyphenysulfonyl)ethenyl)arylenes, which were prepared through aldol-type condensation of arylene dialdehydes with arylmethyl p-methoxypheny sulfones. By varying the combination of dialdehydes and arylmethyl p-methoxypheny sulfones, a series of helicene homologues, ranging from [5] to [7]helicenes, were obtained. The p-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, FeCl3-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[g,p]chrysene arrays.
The Journal of Organic Chemistry
American Chemical Society (ACS)
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