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Cyclophanes, XLII. The Acid-Catalyzed Isomerization of Perhydro[2.2]paracyclophane – A Surprising Out-In Hydrogen Transfer Process

✍ Scribed by Ernst, Ludger ;Hopf, Henning ;Savinsky, Rainer


Publisher
John Wiley and Sons
Year
1997
Tongue
English
Weight
373 KB
Volume
1997
Category
Article
ISSN
0947-3440

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✦ Synopsis


Abstract

Treatment of perhydro[2.2]paracyclophane (1) with trifluoromethanesulfonic acid for 15 h at room temperature in dichloromethane results in a quantitative yield of stereoisomer 2, in which one of the bridgehead hydrogen atoms points towards the inside of the molecule (mono‐endo isomer). The constitution of 2 is derived from 2D‐NMR C,C‐INADE‐QUATE experiments and its stereochemistry from dynamic NMR experiments and molecular mechanics computations (MM3). A mechanism is suggested for the 1–2 interconversion.