Supplementary information files for Organocatalytic enantioselective synthesis of bicyclo[2.2.2]octenones via oxaziridinium catalysed ortho‐hydroxylative phenol dearomatization

Supplementary information files for article Organocatalytic enantioselective synthesis of bicyclo[2.2.2]octenones via oxaziridinium catalysed ortho‐hydroxylative phenol dearomatization <br> Hydroxylative dearomatization reactions of phenols (HPD) offer an efficient way to assemble complex, biologically relevant scaffolds. Despite this, enantioselective hydroxylative phenol dearomatizations for the construction of bicyclo[2.2.2]octenones are classically limited to stoichiometric chiral reagents, and a practical, enantioselective catalytic method has remained elusive. Herein, we describe a highly enantioselective, organocatalytic tandem o-HPD-[4+2] reaction. Our methodology utilizes a chiral oxaziridinium organocatalyst, that is available in both enantiomeric forms, to afford dearomatized products in high enantioselectivity over a range of phenol substitution patterns. This approach was applied to the highly enantioselective synthesis of (+)-biscarvacrol (99 : 1 e.r.) and (−)-bis(2,6-xylenol) (94 : 6 e.r.). The practicality of our conditions was demonstrated at gram-scale, using an amine precatalyst, accessible in a single synthetic step. <br> <br>