Benzo[3.3]benzo[3.3]benzo- and Naphtho[3.3]benzo[3.3]naphtho- orthocyclophane bis(alcohol)s. Preparations and structures

Shuntaro Mataka, Yoshiharu Mitoma, Tsuyoshi Sawada, Thies Thiemann, Masahiko Taniguchi, Masashi Tashiro

Research output: Contribution to journalArticlepeer-review

7 Citations (Scopus)


anti-Benzo[1,2-h;4,5-h']bis(benzo[1,2-c]bicyclo[4.4.1]undeca-3,8-diene- 11-one) (7a) and bis(naphtho[2,3-c]bicyclo[4.4.1]undeca-3,8-diene-11-one) derivative 7b reacted with Grignard reagents (MeMgI and PhMgBr) to give bis(alcohol)s 10-12 or monoalcohols 13 and 14, depending upon the amount of the reagent used. Similarly, syn-bis(alcohol)s 15-17 and syn-monoalcohols 18 and 19 were obtained in the reaction of syn-benzo[1,2-h;4,5-h']bis(benzo[1,2- c]bicyclo[4.4.1]undeca-3,8-diene-11-one) (9) with the Grignard reagents. The alcohols 10-19 were produced as a mixture of configurational isomers and each isomer was isolated by HPLC. The structures were determined by 1H and 13C NMR spectra, NOE study, and X-ray crystallographic analyses of 12a, 13, and 17a. The triple-layered [3.3][3.3]orthocyclophanes 10-12 take the (twin- chair)/(twin-chair) arrangement and in the structure, the top and the bottom aromatic rings sandwich a central benzo ring. syn-Cyclophanes 15-17 exist as an equilibrium mixture of two equivalent (twin-chair)/(chair-boat)- and (chair-boat)/(twin-chair)-conformers in solution. In the solid, the conformation is fixed, as clarified by X-ray crystallographic analysis of 17a. Because of steric congestion, the central benzene ring in 17a is not planar. Monoalcohols 13-14 and 18-19 have a rigid and layered twin-chair substructure and a flexible chair-boat part. The existence of a through- space interaction between the three stacked aromatic rings of [3.3][3.3]orthocyclophanes 10-12 was determined on the basis of a long wavelength shift in UV spectra, as compared to the spectra of 13-19 having a double-layered [3.3]orthocyclophane-substructure.

Original languageEnglish
Pages (from-to)5171-5186
Number of pages16
Issue number20
Publication statusPublished - May 14 1998
Externally publishedYes

ASJC Scopus subject areas

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry


Dive into the research topics of 'Benzo[3.3]benzo[3.3]benzo- and Naphtho[3.3]benzo[3.3]naphtho- orthocyclophane bis(alcohol)s. Preparations and structures'. Together they form a unique fingerprint.

Cite this