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. 2018 Jun 28;74(26):3266-3272.
doi: 10.1016/j.tet.2018.03.052. Epub 2018 Mar 26.

Enantioselective counter-anions in photoredox catalysis: the asymmetric cation radical Diels-Alder reaction

Peter D Morse  1 , Tien M Nguyen  1 , Cole L Cruz  1 , David A Nicewicz  1
Affiliations

Enantioselective counter-anions in photoredox catalysis: the asymmetric cation radical Diels-Alder reaction

Peter D Morse et al. Tetrahedron. .

Abstract

Control of absolute stereochemistry in radical and ion radical transformations is a major challenge in synthetic chemistry. Herein, we report the design of a photoredox catalyst system comprised of an oxidizing pyrilium salt bearing a chiral N-triflyl phosphoramide anion. This class of chiral organic photoredox catalysts is able to catalyze the formation of cation radical-mediated Diels-Alder transformations in up to 75:25 e.r. in both intramolecular and intermolecular examples.

Keywords: catalysis; chiral anion; cycloaddition; enantioselective; photoredox.

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Figures

Figure 1
Figure 1
Scope of the intramolecular enantioselective cation radical Diels-Alder reaction
Figure 2
Figure 2
Scope of the intermolecular enantioselective on radical Diels-Alder reaction
Scheme 1
Scheme 1
Asymmetric photoredox catalysis – prior art
Scheme 2
Scheme 2
The cation radical Diels-Alder reaction and current work
See this image and copyright information in PMC

References

    1. For recent reviews on photoredox catalysis see: Romero NA, Nicewicz DA. Chem Rev. 2016;116:10075–10166.Prier CK, Rankic DA, MacMillan DWC. Chem Rev. 2013;113:5322–5363.Shaw MH, Twilton J, MacMillan DWC. J Org Chem. 2016;81:6898–6926.

    1. Nicewicz DA, MacMillan DWC. Science. 2008;322:77–80. - PMC - PubMed
    2. Nagib DA, Scott ME, MacMillan DWC. J Am Chem Soc. 2009;131:10875–10877. - PMC - PubMed
    3. Shih HW, Vander Wal MN, Grange RL, MacMillan DWC. J Am Chem Soc. 2010;132:13600–13603. - PMC - PubMed
    4. Welin ER, Warkentin AA, Conrad JC, MacMillan DWC. Angew Chem Int Ed. 2015;54:9668–9672. - PMC - PubMed
    1. Du J, Skubi KL, Schultz DM, Yoon TP. Science. 2014;344:392–397. - PMC - PubMed
    2. Amador AG, Sherbrook EM, Yoon TP. J Am Chem Soc. 2016;138:4722–4725. - PMC - PubMed
    1. Huo H, Shen X, Wang C, Zhang L, Röse P, Chen LA, Harms K, Marsch M, Hilt G, Meggers E. Nature. 2014;515:100–103. - PubMed
    2. Huo H, Huang X, Shen X, Harms K, Meggers E. Synlett. 2016;27:749–753.
    3. Huang X, Webster RD, Harms K, Meggers E. J Am Chem Soc. 2016;138:12636–12642. - PubMed
    1. Rono LJ, Yayla HG, Wang DY, Armstrong MF, Knowles RR. J Am Chem Soc. 2013;135:17735–17738. - PubMed

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