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Review
. 2019 Aug 16;10(36):8285-8291.
doi: 10.1039/c9sc03359a. eCollection 2019 Sep 28.

Reductive radical-polar crossover: traditional electrophiles in modern radical reactions

Lena Pitzer  1 , J Luca Schwarz  1 , Frank Glorius  1
Affiliations
Review

Reductive radical-polar crossover: traditional electrophiles in modern radical reactions

Lena Pitzer et al. Chem Sci. .

Abstract

The concept of reductive radical-polar crossover (RRPCO) reactions has recently emerged as a valuable and powerful tool to overcome limitations of both radical and traditional polar chemistry. Especially in case of additions to carbonyl compounds, the synergy of radical and polar pathways is of great advantage since it enables the use of traditional carbonyl electrophiles in radical reactions. The most recent and synthetically important transformations following this line are summarised in the first part of this review. The second part deals with transformations, in which the concept of RRPCO promotes the usage of alkyl halides as electrophiles in radical reactions.

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Figures

Scheme 1
Scheme 1. Strategies to convert carbonyls to alcohols.
Scheme 2
Scheme 2. Approach to use carbonyls as intermolecular radical acceptors by Glorius.
Scheme 3
Scheme 3. Photoredox-mediated dicarbofunctionalization of styrenes by Martin.
Scheme 4
Scheme 4. Cerium- and photoredox-mediated bridged lactonisation by Zuo.
Scheme 5
Scheme 5. α-Carboxylation of enamindes and imines by Yu.
Scheme 6
Scheme 6. Cross-electrophile coupling by Yu.
Scheme 7
Scheme 7. Benzylation of aliphatic aldehydes by König.
Scheme 8
Scheme 8. Photocarboxylation of benzylic C–H bonds by König.
Scheme 9
Scheme 9. Polycyclisation for the synthesis of terpenoids by Pronin.
Scheme 10
Scheme 10. Branch-selective addition of olefins to aliphatic aldehydes by Shenvi.
Scheme 11
Scheme 11. Decarboxylative Nozaki–Hiyama–Kishi reaction by Baran.
Scheme 12
Scheme 12. Diastereoselective allylation of aldehydes by Glorius.
Scheme 13
Scheme 13. Asymmetric allylation of aldehydes by Kanai.
Scheme 14
Scheme 14. Cyclopropanation by Molander.
Scheme 15
Scheme 15. Cyclopropanation by Aggarwal.
None
Lena Pitzer
None
J. Luca Schwarz
None
Frank Glorius
See this image and copyright information in PMC

References

    1. Studer A., Curran D. P. Angew. Chem., Int. Ed. 2016;55:58–102. - PubMed
    1. Leifert D., Studer A. Angew. Chem., Int. Ed. 2019 doi: 10.1002/anie.201903726. - DOI - PubMed

    1. For selected examples, see:

    2. Wang C., Qin J., Shen X., Riedel R., Harms K., Meggers E. Angew. Chem., Int. Ed. 2016;55:685–688. - PubMed
    3. Li W., Duan Y., Zhang M., Cheng J., Zhu C. Chem. Commun. 2016;52:7596–7599. - PubMed
    4. Berger A. L., Donabauer K., König B. Chem. Sci. 2018;9:7230–7235. - PMC - PubMed
    5. Ding W., Lu L.-Q., Liu J., Liu D., Song H.-T., Xiao W.-J. J. Org. Chem. 2016;81:7237–7243. - PubMed
    6. Petronijević F. R., Nappi M., MacMillan D. W. C. J. Am. Chem. Soc. 2013;135:18323–18326. - PMC - PubMed
    7. Du J., Skubi K. L., Schultz D. M., Yoon T. P. Science. 2014;344:392–396. - PMC - PubMed
    8. Rono L. J., Yayla H. G., Wang D. Y., Armstrong M. F., Knowles R. R. J. Am. Chem. Soc. 2013;135:17735–17738. - PubMed
    9. Nakajima M., Fava E., Loescher S., Jiang Z., Rueping M. Angew. Chem., Int. Ed. 2015;54:8828–8832. - PubMed
    1. Roth H. G., Romero N. A., Nicewicz D. A. Synlett. 2016;27:714–723.

    1. For selected examples, see:

    2. Clerici A., Porta O., Zago P. Tetrahedron. 1986;42:561–572.
    3. Clerici A., Porta O. J. Org. Chem. 1989;54:3872–3878.