Isothiourea-catalyzed enantioselective addition of 4-nitrophenyl esters to iminium ions

Jude N. Arokianathar, Aileen B. Frost, Alexandra M. Z. Slawin, Darren Stead, Andrew D. Smith

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Isothioureas catalyze the enantioselective addition of 4-nitrophenyl esters to tetrahydroisoquinoline-derived iminium ions. 4-Nitrophenoxide, generated in situ from initial N-acylation of the isothiourea by the 4-nitrophenyl ester, is used to facilitate catalyst turnover in this reaction process. Optimization showed that 4-nitrophenyl esters give the best reactivity in this protocol over a range of alternative aryl esters, with the observed enantioselectivity markedly dependent upon the nature of the iminium counteri-on. Highest yields and enantioselectivity were obtained using iminium bromide ions generated in situ via photoredox catalysis using BrCCl3 and Ru(bpy)3Cl2 (0.5 mol%) and commercially available tetramisole (5 mol%) as the Lewis base catalyst. The scope and limitations of this procedure was developed, giving the desired β-amino amide products in up to 96% yield, 79:21 dr and ermajor (2R,1′S) 99.5:0.5.
Original languageEnglish
Pages (from-to)1153-1160
JournalACS Catalysis
Issue number2
Early online date12 Dec 2017
Publication statusPublished - 2 Feb 2018


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