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Contents Vol 63(12)

Mixed [2.2]Cyclophanes of Pyrene and Benzene

Rudolf J. Vermeij A , David O. Miller B , Louise N. Dawe B , Ivan Aprahamian C D , Tuvia Sheradsky C E , Mordecai Rabinovitz C and Graham J. Bodwell A F
+ Author Affiliations
- Author Affiliations

A Department of Chemistry, Memorial University, St. John’s, NL A1B 3X7, Canada.

B CREAIT Network, Memorial University, St. John’s, NL A1B 3S5, Canada.

C Institute of Chemistry, The Hebrew University of Jerusalem, Jerusalem 91904, Israel.

D Present address: Department of Chemistry, Dartmouth College, 6128 Burke Laboratory, Hanover, NH 03755, USA.

E Deceased.

F Corresponding author. Email: gbodwell@mun.ca

Australian Journal of Chemistry 63(12) 1703-1716 https://doi.org/10.1071/CH10356
Submitted: 28 September 2010  Accepted: 22 October 2010   Published: 6 December 2010

Abstract

An examination of the literature on [2.2]cyclophanes reveals a loose relationship between the relative sizes of the two ‘half-cyclophanes’ (as measured by the parameter Δd) and the limitations of the dominant general synthetic approaches. Direct coupling methods tend to be successful only for systems with Δd values below 1.0 Å, whereas ring-contraction-based approaches are usually viable for systems with Δd values up to 2.0 Å. For the very few known systems with Δd values greater than 2.0 Å, aromatization-based approaches are the only ones that have been successful. The syntheses of two [2.2]cyclophanes with very large Δd values, [2]paracyclo[2](2,7)pyrenophane (17) (Δd = 4.25 Å) and [2]metacyclo[2](2,7)pyrenophane (18) (Δd = 5.04 Å) are presented here. The syntheses hinge on a valence isomerization/dehydrogenation reaction. The crystallographically determined bend angle, θ, for 18 is 96.1°. Cyclophane 18 undergoes a degenerate conformational flip, the energy barrier for which was determined to be 18.9 kcal mol–1 by DNMR.


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