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

Research output: Contribution to journalArticlepeer-review

26 Citations (Scopus)

Abstract

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.

Original languageEnglish
Pages (from-to)16526-16532
Number of pages7
JournalJournal of the American Chemical Society
Volume135
Issue number44
DOIs
Publication statusPublished - 2013 Nov 6

ASJC Scopus subject areas

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

Fingerprint

Dive into the research topics of 'Equatorenes: Synthesis and properties of chiral naphthalene, phenanthrene, chrysene, and pyrene possessing bis(1-adamantyl) groups at the peri-position'. Together they form a unique fingerprint.

Cite this