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Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst
Published on: April 22, 2016
Combining the catalytic enantioselective reaction of visible-light-generated radicals with a by-product utilization
Xiaoqiang Huang1, Shipeng Luo1, Olaf Burghaus1
1Fachbereich Chemie , Philipps-Universität Marburg , Hans-Meerwein-Strasse 4 , 35043 Marburg , Germany .
Abstract:
We report an unusual reaction design in which a chiral bis-cyclometalated rhodium(iii) complex enables the stereocontrolled chemistry of photo-generated carbon-centered radicals and at the same time catalyzes an enantioselective sulfonyl radical addition to an alkene. Specifically, employing inexpensive and readily available Hantzsch esters as the photoredox mediator, Rh-coordinated prochiral radicals generated by a selective photoinduced single electron reduction are trapped by allyl sulfones in a highly stereocontrolled fashion, providing radical allylation products with up to 97% ee. The hereby formed fragmented sulfonyl radicals are utilized via an enantioselective radical addition to form chiral sulfones, which minimizes waste generation.
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