Highly Selective Photomediated 1,4‐Radical Addition to o‐Quinones Controlled by a Self‐Assembled Cage

Abstract

Cavity control: A highly selective 1,4‐addition reaction of a toluene derivative to o‐quinones proceeds efficiently within a self‐assembled coordination cage (see scheme). The cage accelerates the formation of the 1,4‐adduct but suppresses all other reaction pathways that are normally favorable in the absence of the cage.

Supramolecular Coordination: Self-Assembly of Finite Two- and Three-Dimensional Ensembles

“…The photomediated 1,4-radical addition of o -quinones to a bulky toluene derivative was also observed within the cavity of self-assembled host 286 . 604 The photoexcited quinone abstracts a proton from the neighbouring methyl group of the toluene derivative to generate a benzylic radical and semiquinone radicals, which subsequently recombine to selectively produce the 1,4-adduct in 70% yield.…”

Designing ‘Totem’ C2‐Symmetrical Iron Porphyrin Catalysts for Stereoselective Cyclopropanations

“…Note that the eco‐tolerability of cyclopropanation reactions can be further enhanced i) by using continuous flow methodologies due to the safe handling of hazardous reagents such as diazo compounds, ii) by applying biomimetic catalysts coupling very good catalytic activity with natural high chemical selectivity, and iii) by employing unconventional catalytic systems such as supramolecular cage catalysts which simulate the working operandi of enzymes …”

Syntheses and molecular structures of half-sandwich iridium metallarectangles containing bridging 2,5-dihydroxy-1,4- benzoquinonato (dhbq) ligands

“…After the first case of molecular square [{Pd(en)(l-4,4 0 -bipy)} 4 ](NO 3 ) 8 reported by Fujita and coworkers in 1990 [5], a series of supramolecules with platinum or palladium were developed in host-guest chemistry -encapsulating compounds, recognizing or trapping guest molecules, microreactors for specific reactions [6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24]. Using metal centers as corners and organic linkers in the build up of molecular architectures led to materials with new properties.…”