Equatorenes: Synthesis and properties of chiral naphthalene, phenanthrene, chrysene, and pyrene possessing bis(1-adamantyl) groups at the peri-position

Koji Yamamoto, Naohiro Oyamada, Sheng Xia, Yuta Kobayashi, Masahiko Yamaguchi, Hiroaki Maeda, Hiroshi Nishihara, Tadafumi Uchimaru, Eunsang Kwon

研究成果: Article査読

25 被引用数 (Scopus)

抄録

Chiral polycyclic aromatic hydrocarbons containing bis(1-adamantyl) groups at the peri-positions, named equatorenes, were synthesized in optically pure form starting from optically pure 4,5-bis(1-adamantyl)-8-methoxy-1-naphthol. A sequential Diels-Alder reaction of furan and arynes generated from 1,2-bromotriflates provided tricyclic and tetracyclic epoxides, and acid-catalyzed aromatization gave phenanthrol and chrysenol. Deoxygenation reactions involving the hydrogenolysis of triflates gave 1,8-bis(1-adamantyl) naphthalene, 1,10-bis(1-adamantyl)phenanthrene, and 1,12-bis(1-adamantyl) chrysene. 3,4-Bis(1-adamantyl)pyrene was synthesized from phenanthrol by Sonogashira coupling and Pt-catalyzed cyclization. Essentially no racemization occurred during the synthesis. X-ray analysis indicated the distorted naphthalene moiety possessing the peri-diadamantyl groups and the flat structure of the other benzene rings. UV-vis analysis of the equatorenes showed considerable redshifts compared with that of the corresponding achiral arenes. Electrochemical analysis of the naphthalene and pyrene indicated that the distortion decreased the highest occupied molecular orbital stability with no marked effect on the lowest unoccupied molecular orbital energy level, and the origin was discussed on the basis of calculation results.

本文言語English
ページ(範囲)16526-16532
ページ数7
ジャーナルJournal of the American Chemical Society
135
44
DOI
出版ステータスPublished - 2013 11 6

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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