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DMAP‐[2.2]paracyclophane: Observation of an Unusual C–C Insertion
Author(s) -
De Rycke Nicolas,
Marrot Jérôme,
Couty François,
David Olivier R. P.
Publication year - 2011
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201001623
Subject(s) - enantiopure drug , moiety , chemistry , diastereomer , cyclophane , catalysis , pyridine , nucleophile , chirality (physics) , stereochemistry , amine gas treating , nucleophilic addition , crystallography , medicinal chemistry , organic chemistry , enantioselective synthesis , crystal structure , chiral symmetry , physics , nambu–jona lasinio model , quantum mechanics , quark
A novel family of nucleophilic catalysts derived from 4‐(dimethylamino)pyridine (DMAP) is described. The aminopyridine moiety is attached to a [2.2]paracyclophane skeleton, giving a catalyst with intrinsic planar chirality. Their synthesis is described starting from aminoparacyclophane 5 in four steps. In the course of this preparation, an unprecedented rearrangement involving a C–C bond insertion was observed, leading to an unexpected quinolone‐phenyl[2.2]cyclophane ( 8 ). The target catalyst 16 was obtained in enantiopure form by formation of diastereomers with a chiral secondary amine, allowing simple chromatographic separation. Preliminary catalytic studies were also performed.