Regio- and Atroposelective Ring-Opening of 1H-Benzo[4,5]oxazolopyridinones.

The development of new methods for regio- and stereoselective activation of C-O bonds in ethers holds significant promise for synthetic chemistry, offering advantages in terms of environmental sustainability and economic efficiency. Moreover, the C-N atropisomers represent a fascinating and crucial chiral system, extensively found in natural products, pharmaceutical leads, and the frameworks of advanced materials. In this work, we have introduced a nickel-catalyzed regio- and enantioselective carbon-oxygen arylation reaction for atroposelective synthesis of N-arylisoquinoline-1,3(2H,4H)-diones. The high regioselectivity of C-O cleavage benefits from the high stability of the in situ formed (amido)ethenolate via oxidative addition. Additionally, the self-activation of the aryl C-O bond facilitates the reaction under mild conditions, leading to outstanding enantioselectivities. The diverse post-functionalizations of the axially chiral isoquinoline-1,3(2H,4H)-diones further highlighted the utility of this protocol in preparing valuable C-N atropisomers, including the chiral phosphine ligands.

Photolysis of the BODIPY dye activated by pillar[5]arene.

Here, a pseudo[3]rotaxane comprising a fluorescent BODIPY derivative and pillar[5]arene was conveniently fabricated via host-guest complexation. Importantly, in this system, the efficient photodecomposition of the BODIPY derivative in the presence of pillar[5]arene was witnessed upon irradiation at 311 nm light, which was demonstrated via UV-Vis absorption, fluorescence emission, NMR and HR-MS spectroscopy techniques, but the only BODIPY dye in the absence of pillar[5]arene couldn't undergo photodegradation. We demonstrated that pillar[5]arene could act as an activator to trigger the photodegradation reaction of BODIPY derivatives via free radical reactions even without supramolecular interactions. The present results provide a new strategy for the efficient photolysis of organic dyes.