Reported here is the first catalytic atroposelective electrophilic amination of indoles, which delivers functionalized atropochiral N-sulfonyl-3-arylaminoindoles with excellent optical purity. This reaction was furnished by 1,6-nucleophilic addition to p-quinone diimines. Control experiments suggest an ionic mechanism that differs from the radical addition pathway commonly proposed for 1,6-addition to quinones. The origin of 1,6-addition selectivity was investigated through computational studies. Preliminary studies show that the obtained 3-aminoindoles atropisomers exhibit anticancer activities. This method is valuable with respect to enlarging the toolbox for atropochiral amine derivatives.
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Article Synopsis
- The paper discusses the challenges in creating axially chiral compounds using gold(I) catalysis, particularly in asymmetric synthesis, which has seen limited progress.
- A new method is introduced that utilizes gold/HNTf cocatalysis for asymmetric diazo-alkyne annulation, successfully producing chiral biaryls and arylquinones with high yields and enantioselectivity.
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