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From [10]Paracyclophane to Ferrocenophanones: The Search for Molecular Machines and Bio‐Organometallic Anticancer Drugs
Author(s) -
McGlinchey Michael J.,
Milosevic Sandra
Publication year - 2012
Publication title -
israel journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.908
H-Index - 54
eISSN - 1869-5868
pISSN - 0021-2148
DOI - 10.1002/ijch.201100080
Subject(s) - chemistry , allene , moiety , cyclophane , isomerization , intramolecular force , stereochemistry , eribulin , ruthenium , organic chemistry , molecule , medicine , metastatic breast cancer , cancer , breast cancer , catalysis
A partial quenching of the NMR ring current in [10]paracyclophane‐chromium tricarbonyl prompted a study of other metal–arene π complexes, several of which exhibited restricted intramolecular motion relevant to their potential use in molecular machines. An attempted Diels–Alder reaction of 9‐phenylethynyl‐9 H ‐fluorene with tetracyclone instead yielded a novel tetracene by isomerization of the alkyne to the corresponding allene, and then via a series of allene dimers which are classifiable as cyclophanes. (Subsequently, the first organometallic molecular brake was prepared, whereby migration of a metal carbonyl tripod over an indenyl framework blocked the rotation of a triptycene paddlewheel.) Cyclophanes have now found applicability in the field of bio‐organometallic chemistry; the activity of tamoxifen, the first line treatment for hormone‐dependent breast cancers, is markedly enhanced when the structure is modified by incorporation of a ferrocenophane moiety. Finally, we relate the story of how the first cyclophane, [1.1.1]orthocyclophane, was actually prepared by Cannizzaro in 1854, but was only recognized as such more than 150 years later.