Asymmetric Hydroxylative Phenol Dearomatization Promoted by Chiral Binaphthylic and Biphenylic Iodanes1. (22nd July 2014)

• Record Type: Journal Article
• Authors: Bosset, Cyril; Coffinier, Romain; Peixoto, Philippe A.; El Assal, Mourad; Miqueu, Karinne; Sotiropoulos, Jean‐Marc; Pouységu, Laurent; Quideau, Stéphane
• Is Part Of: Angewandte Chemie. Volume 126:Number 37(2014)
• Page Start: 10018
• Page End: 10022
• Publication Date: 2014-07-22
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201403571
• Languages: English
• ISSNs: 0044-8249

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>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 <italic>ortho</italic>‐quinol‐based [4+2] cyclodimer (i.e., bis(thymol)) with enantiomeric excesses of up to 94 %.</p> </abstract>