One‐Pot Enantioselective Synthesis of 1,4‐Naphthoquinone‐Derived Polycycles through Oxidative Dearomatization and Aminocatalysis

Abstract

A synthetic process merging oxidative dearomatization and asymmetric aminocatalysis in a single vessel is reported. The PhI(OAc) 2 -mediated oxidation of 1,4-dihydroxynaphthalene is followed by a trienamine-mediated Diels-Alder cycloaddition/aldol reaction or a trienamine-mediated Diels-Alder cycloaddition/oxidation sequence depending on the dienal substitution pattern. The polycyclic compounds are obtained

Atom Economical Photocatalytic Oxidation of Phenols and Site-Selective Epoxidation Toward Epoxyquinols

“…The photooxygenation of phenols offers straightforward synthetic routes toward quinones or cyclohexadienone motifs, which are interesting building blocks used to reach polyoxygenated targets such as epoxyquinol structures (Scheme ). The structural complexity and diverse biological activities of epoxyquinols make them attractive targets for total synthesis . A convenient strategy to reach substituted epoxyquinols involves a multistep sequence, namely photooxygenation/reduction/epoxidation, starting from para -substituted phenols (Scheme a) .…”

Aminocatalyzed Synthesis of Enantioenriched Phenalene Skeletons through a Friedel–Crafts/Cyclization Strategy

“…As a part of our ongoing interest into organocatalytic functionalization of aromatic architectures, we recently developed an efficient protocol for the aminocatalyzed cascade synthesis of enantioenriched 1,7-annulated indoles and indazoles from α,β-unsaturated aldehydes (Scheme a) . Taking advantage of the ability of aminocatalysts to promote iminium/enamine cascade sequences in the presence of α,β-unsaturated aldehydes, the synthetic strategy toward 1,7-annulated heterocycles involved an aza-Michael reaction followed by an intramolecular aldol condensation.…”

Construction of spirocarbocycles via gold-catalyzed intramolecular dearomatization of naphthols

“… 4 , 5 Particularly, dearomatization reactions of phenol and derivatives have been much under-developed despite potential direct access to highly functionalized spirocarbocycles. 6 , 7 In this regard, Hamada and coworkers recently reported an elegant gold-catalyzed 5- exo-dig carbocyclization of phenols in the presence of methanesulfonic acid and 2,6-di- tert -butylpyridine. 6 b Interestingly, we found 5- endo-dig cyclization products could be selectively obtained via gold-catalyzed dearomatizations of naphthols under mild conditions.…”