NMR studies of cyclophanes  L. Ernst * Department of Chemistry, Technical University of Braunschweig, Hagenring 30, D-38106 Braunschweig, Germany Received 17 January 2000 Contents 1. Introduction and scope ........................................................... 48 2. [n]Phanes .................................................................... 49 2.1. [n]Metacyclophanes ........................................................ 49 2.2. [n]Paracyclophanes ......................................................... 55 2.3. Other [n]phanes ........................................................... 65 2.4. [1.n]Phanes ............................................................... 71 3. [2.2]Phanes ................................................................... 73 3.1. [2.2]Metacyclophanes ....................................................... 73 3.2. [2.2]Paracyclophanes ....................................................... 83 3.3. [2.2]Metaparacyclophanes .................................................... 95 3.4. [2.2]Orthometacyclophanes ................................................... 97 3.5. [2.2]Orthoparacyclophanes ................................................... 99 3.6. [2.2]Naphthalenophanes ..................................................... 99 3.7. Other [2.2]phanes .......................................................... 100 3.8. [2.2]Heterophanes .......................................................... 108 3.9. [2.2]- and [3.3]Phanes capable of through-space 19 F, 19 F coupling ....................... 115 4. [3.3]Phanes ................................................................... 119 4.1. [3.3]Phane hydrocarbons ..................................................... 119 4.1.1. [3.3]Metacyclophanes ................................................. 119 4.1.2. [3.3]Paracyclophanes .................................................. 125 4.1.3. [3.3]Metaparacyclophanes .............................................. 127 4.1.4. Other [3.3]cyclophanes ................................................ 127 4.2. Dithia- and diaza[3.3]phanes .................................................. 128 4.2.1. Dithia- and diaza[3.3]metacyclophanes ..................................... 128 4.2.2. Dithia- and diaza[3.3]paracyclophanes ..................................... 133 4.2.3. Other dithia- and diaza[3.3]phanes ........................................ 133 5. [m.n]Phanes (m  2, n  2) ....................................................... 145 6. Multiply bridged phanes ......................................................... 159 6.1. Phanes with multiple bridges between different aromatic rings ......................... 159 Progress in Nuclear Magnetic Resonance Spectroscopy 37 (2000) 47–190 0079-6565/00/$ - see front matter  2000 Elsevier Science B.V. All rights reserved. PII: S0079-6565(00)00022-4 www.elsevier.nl/locate/pnmrs  I dedicate this review to my parents on the occasion of my mother’s 86th and my father’s 85th birthday in November 1999. * Tel.: +49-531-3915379; fax: +49-531-3915387. E-mail address: l.ernst@tu-bs.de (L. Ernst).