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Professor Bruce Lipshutz Professor David Nicewicz

The Nicewicz lab is focused on the discovery of new and powerful reaction methodologies that proceed via the intermediacy of highly reactive cation radical species. Included in these transformations are anti-Markovnikov selective additions of amines, alcohols, carboxylic acids, amides and mineral acids to alkenes. The key reactive intermediates, alkene cation radicals, are generated via single electron oxidation by photoexcited acridinium salts, first developed by Shunichi Fukuzumi. A range of acridinium catalysts have been established for this purpose, all of which are air and moisture stable and have oxidizing capabilities all significantly higher (>+2.0 V vs. SCE) than their Ru- and Ir- polypyridyl counterparts. Excitation of the acridinium salts can be accomplished easily in batch or in flow using 450 nm LED flood lamps. In conjunction with either thiol or disulfide co-catalysts, anti-Markovnikov additions of acids to styrenes, trisubstituted aliphatic alkenes and enamides are possible. If allylic alcohols or α,β-unsaturated carboxylic acids are partnered with alkenes, highly substituted tetrahydrofurans and butyrolactone products can be formed, respectively, via polar radical crossover cycloadditions. The Nicewicz lab continues to develop new transformations based on the generic acridinium catalyst platform with the goal of operational simplicity.

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Tien M Nguyen, David A Nicewicz
Journal of the American Chemical Society 2013-07-03
Herein we report a metal-free method for the direct anti-Markovnikov hydroamination of unsaturated amines. Irradiation of the amine substrates with visible light in the presence of catalytic quantities of easily synthesized 9-mesityl-10-methylacridinium tetrafluoroborate and thiophenol as a hydrogen-atom donor furnished the nitr...Read More
Dale J Wilger, Jean-Marc M Grandjean, Taylor R Lammert, David A Nicewicz
Nature Chemistry 2014-08-01
The direct anti-Markovnikov addition of strong Brønsted acids to alkenes remains an unsolved problem in synthetic chemistry. Here, we report an efficient organic photoredox catalyst system for the addition of HCl, HF and also phosphoric and sulfonic acids to alkenes, with complete regioselectivity. These transformations were dev...Read More
Andrew J Perkowski, David A Nicewicz
Journal of the American Chemical Society 2013-07-17
A direct catalytic anti-Markovnikov addition of carboxylic acids to alkenes is reported. The catalyst system is comprised of the Fukuzumi acridinium photooxidant (1) and a substoichiometric quantity of a hydrogen-atom donor. Oxidizable olefins, such as styrenes, trisubstituted aliphatic alkenes, and enamides, can be employed alo...Read More
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