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From Central to Helical Chirality: Synthesis of P and M Enantiomers of [5]Helicenequinones and Bisquinones from (S S )‐2‐( p ‐Tolylsulfinyl)‐ 1,4‐benzoquinone
Author(s) -
Carreño M. Carmen,
GarcíaCerrada Susana,
Urbano Antonio
Publication year - 2003
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200304835
Subject(s) - enantiopure drug , aromatization , helicene , chemistry , enantiomer , sulfoxide , chirality (physics) , stereochemistry , stereospecificity , domino , cycloaddition , medicinal chemistry , enantioselective synthesis , molecule , organic chemistry , catalysis , nambu–jona lasinio model , chiral symmetry breaking , physics , quantum mechanics , quark
The reaction of 1,4‐divinyl‐1,3‐cyclohexadiene, 5,8‐dimethoxy‐ or tert‐ butyldimethylsilyloxy‐3‐vinyl‐1,2‐dihydrophenanthrene or 6‐vinyl‐7,8‐dihydro‐1,4‐phenanthrenequinone with an excess of enantiopure (S S )‐2‐( p ‐tolylsulfinyl)‐1,4‐benzoquinone ( 2 ) led to the direct formation of enantioenriched dihydro[5]helicenequinones or bisquinones (50→98 % ee ). A domino Diels–Alder cycloaddition/sulfoxide elimination/partial aromatization process occurs, being the absolute configuration of the final helicene defined in the aromatization step. Both M and P helimers are accessible through a stepwise enantiodivergent process if the pentacyclic dihydroaromatic intermediate resulting in the two first steps is aromatized in the presence of (±)‐ 2 , DDQ, CAN or DBU.