Asymmetric Hydroxylative Phenol Dearomatization Promoted by Chiral Binaphthylic and Biphenylic Iodanes†
Cyril Bosset
Univ. Bordeaux, ISM (CNRS-UMR 5255) and IECB, 2 rue Robert Escarpit, 33607 Pessac Cedex (France)
These authors contributed equally to this work.
Search for more papers by this authorRomain Coffinier
Univ. Bordeaux, ISM (CNRS-UMR 5255) and IECB, 2 rue Robert Escarpit, 33607 Pessac Cedex (France)
These authors contributed equally to this work.
Search for more papers by this authorDr. Philippe A. Peixoto
Univ. Bordeaux, ISM (CNRS-UMR 5255) and IECB, 2 rue Robert Escarpit, 33607 Pessac Cedex (France)
Search for more papers by this authorMourad El Assal
Univ. Bordeaux, ISM (CNRS-UMR 5255) and IECB, 2 rue Robert Escarpit, 33607 Pessac Cedex (France)
Search for more papers by this authorDr. Karinne Miqueu
Univ. Pau et Pays de l'Adour, IPREM (CNRS-UMR 5254), Hélioparc, 2 avenue Pierre Angot, 64053 Pau Cedex 09 (France)
Search for more papers by this authorDr. Jean-Marc Sotiropoulos
Univ. Pau et Pays de l'Adour, IPREM (CNRS-UMR 5254), Hélioparc, 2 avenue Pierre Angot, 64053 Pau Cedex 09 (France)
Search for more papers by this authorCorresponding Author
Dr. Laurent Pouységu
Univ. Bordeaux, ISM (CNRS-UMR 5255) and IECB, 2 rue Robert Escarpit, 33607 Pessac Cedex (France)
Univ. Bordeaux, ISM (CNRS-UMR 5255) and IECB, 2 rue Robert Escarpit, 33607 Pessac Cedex (France)Search for more papers by this authorCorresponding Author
Prof. Stéphane Quideau
Univ. Bordeaux, ISM (CNRS-UMR 5255) and IECB, 2 rue Robert Escarpit, 33607 Pessac Cedex (France)
Univ. Bordeaux, ISM (CNRS-UMR 5255) and IECB, 2 rue Robert Escarpit, 33607 Pessac Cedex (France)Search for more papers by this authorCyril Bosset
Univ. Bordeaux, ISM (CNRS-UMR 5255) and IECB, 2 rue Robert Escarpit, 33607 Pessac Cedex (France)
These authors contributed equally to this work.
Search for more papers by this authorRomain Coffinier
Univ. Bordeaux, ISM (CNRS-UMR 5255) and IECB, 2 rue Robert Escarpit, 33607 Pessac Cedex (France)
These authors contributed equally to this work.
Search for more papers by this authorDr. Philippe A. Peixoto
Univ. Bordeaux, ISM (CNRS-UMR 5255) and IECB, 2 rue Robert Escarpit, 33607 Pessac Cedex (France)
Search for more papers by this authorMourad El Assal
Univ. Bordeaux, ISM (CNRS-UMR 5255) and IECB, 2 rue Robert Escarpit, 33607 Pessac Cedex (France)
Search for more papers by this authorDr. Karinne Miqueu
Univ. Pau et Pays de l'Adour, IPREM (CNRS-UMR 5254), Hélioparc, 2 avenue Pierre Angot, 64053 Pau Cedex 09 (France)
Search for more papers by this authorDr. Jean-Marc Sotiropoulos
Univ. Pau et Pays de l'Adour, IPREM (CNRS-UMR 5254), Hélioparc, 2 avenue Pierre Angot, 64053 Pau Cedex 09 (France)
Search for more papers by this authorCorresponding Author
Dr. Laurent Pouységu
Univ. Bordeaux, ISM (CNRS-UMR 5255) and IECB, 2 rue Robert Escarpit, 33607 Pessac Cedex (France)
Univ. Bordeaux, ISM (CNRS-UMR 5255) and IECB, 2 rue Robert Escarpit, 33607 Pessac Cedex (France)Search for more papers by this authorCorresponding Author
Prof. Stéphane Quideau
Univ. Bordeaux, ISM (CNRS-UMR 5255) and IECB, 2 rue Robert Escarpit, 33607 Pessac Cedex (France)
Univ. Bordeaux, ISM (CNRS-UMR 5255) and IECB, 2 rue Robert Escarpit, 33607 Pessac Cedex (France)Search for more papers by this authorFinancial support from the Agence Nationale de la Recherche (ANR-10-BLAN-0721), the CNRS, the Conseil Régional d′Aquitaine, and the French Ministry of Research, including doctoral assistantships for C.B., R.C., and M.E.A., is gratefully acknowledged. The authors also wish to thank Dr. J. Brioche for his contribution to the elaboration of this research project.
Graphical Abstract
The selective oxygenation of iodobinaphthyls and iodobiphenyls afforded either λ3- or λ5-iodanes, which were evaluated for their capacity to promote asymmetric intermolecular hydroxylative phenol dearomatizations (HPDs). Most remarkably, a C2-symmetrical biphenylic λ5-iodane induced the HPD reaction/[4+2] cyclodimerization cascade of thymol into bis(thymol) with enantiomeric excesses of up to 94 %.
Abstract
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 λ3- or λ5-iodanes, and the evaluation of their capacity to promote asymmetric hydroxylative phenol dearomatization (HPD) reactions. Most notably, a C2-symmetrical biphenylic λ5-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 %.
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