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Asymmetric Hydroxylative Phenol Dearomatization Promoted by Chiral Binaphthylic and Biphenylic Iodanes
Author(s) -
Bosset Cyril,
Coffinier Romain,
Peixoto Philippe A.,
El Assal Mourad,
Miqueu Karinne,
Sotiropoulos JeanMarc,
Pouységu Laurent,
Quideau Stéphane
Publication year - 2014
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201403571
Subject(s) - hypervalent molecule , phenol , reagent , chemistry , enantiomer , enantioselective synthesis , thymol , stoichiometry , organic chemistry , combinatorial chemistry , catalysis , chromatography , essential oil
The long‐standing quest for chiral hypervalent organoiodine compounds (i.e., iodanes) as metal‐free reagents for asymmetric synthesis continues. Although remarkable progress has recently been made in organoiodine‐catalyzed reactions using a terminal oxidant in stoichiometric amounts, there is still a significant need for “flaskable” chiral iodane reagents. Herein, we describe the synthesis of new iodobinaphthyls and iodobiphenyls, their successful and selective DMDO‐mediated oxidation into either λ 3 ‐ or λ 5 ‐iodanes, and the evaluation of their capacity to promote asymmetric hydroxylative phenol dearomatization (HPD) reactions. Most notably, a C 2 ‐symmetrical biphenylic λ 5 ‐iodane promoted the HPD‐induced conversion of the monoterpene thymol into the corresponding ortho ‐quinol‐based [4+2] cyclodimer (i.e., bis(thymol)) with enantiomeric excesses of up to 94 %.