Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2017 Sep 1;7(9):6342-6346.
doi: 10.1021/acscatal.7b02356. Epub 2017 Aug 18.

S,O-Ligand-Promoted Palladium-Catalyzed C-H Functionalization Reactions of Nondirected Arenes

Kananat Naksomboon  1 , Carolina Valderas  1 , Melania Gómez-Martínez  1 , Yolanda Álvarez-Casao  1 , M Ángeles Fernández-Ibáñez  1
Affiliations

S,O-Ligand-Promoted Palladium-Catalyzed C-H Functionalization Reactions of Nondirected Arenes

Kananat Naksomboon et al. ACS Catal. .

Abstract

Pd(II)-catalyzed C-H functionalization of nondirected arenes has been realized using an inexpensive and easily accessible type of bidentate S,O-ligand. The catalytic system shows high efficiency in the C-H olefination reaction of electron-rich and electron-poor arenes. This methodology is operationally simple, scalable, and can be used in late-stage functionalization of complex molecules. The broad applicability of this catalyst has been showcased in other transformations such as Pd(II)-catalyzed C-H acetoxylation and allylation reactions.

Keywords: C−H activation; S,O-ligand; arenes; olefination; palladium.

PubMed Disclaimer

Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1. Kinetic Profile of the Dehydrogenative Heck Coupling of Benzene and Ethyl Acrylate without Ligand and in the Presence of L2
Scheme 2
Scheme 2. Late-Stage C–H Olefination of (a) Estrone and (b) Naproxen Derivatives
Scheme 3
Scheme 3. S,O-Ligand-Promoted Pd-Catalyzed (a) C–H Acetoxylation and (b) Allylation of Benzene
See this image and copyright information in PMC

References

    1. For general reviews on C–H functionalization, see:

    2. Alberico D.; Scott M. E.; Lautens M. Chem. Rev. 2007, 107, 174–238. 10.1021/cr0509760. - DOI - PubMed
    3. Yu J.-Q.; Shi Z.. C–H Activation; Yu J.-Q., Shi Z., Eds.; Topics in Current Chemistry, Vol. 292; Springer: Berlin, 2010. - PubMed
    4. Hartwig J. F. J. Am. Chem. Soc. 2016, 138, 2–24. 10.1021/jacs.5b08707. - DOI - PMC - PubMed
    5. Davies H. M. L.; Morton D. J. Org. Chem. 2016, 81, 343–350. 10.1021/acs.joc.5b02818. - DOI - PubMed

    6. For a special issue dedicated to this topic, see:

    7. Doyle M. P.; Goldberg K. I.. Acc. Chem. Res. 2012, 45, 777.10.1021/ar300096z - DOI - PubMed
    1. Lyons T. W.; Sanford M. S. Chem. Rev. 2010, 110, 1147–1169. 10.1021/cr900184e. - DOI - PMC - PubMed
    2. Chen Z.; Wang B.; Zhang J.; Yu W.; Liu Z.; Zhang Y. Org. Chem. Front. 2015, 2, 1107–1295. 10.1039/C5QO00004A. - DOI
    3. Maes J.; Maes B. U. W. Adv. Heterocycl. Chem. 2016, 120, 137–194. 10.1016/bs.aihch.2016.04.005. - DOI
    4. Pototschnig G.; Maulide N.; Schnürch M. Chem.—Eur. J. 2017, 23, 9206–9232. 10.1002/chem.201605657. - DOI - PubMed
    5. Ma W.; Gandeepan P.; Li J.; Ackermann L. Org. Chem. Front. 2017, 4, 1435–1467. 10.1039/C7QO00134G. - DOI

    1. For a review on C–H functionalization of substrates that do not bear directing groups, see:

    2. Kuhl N.; Hopkinson M. N.; Wencel-Delord J.; Glorius F. Angew. Chem., Int. Ed. 2012, 51, 10236–10254. 10.1002/anie.201203269. - DOI - PubMed

    3. For selected examples, see:

    4. Robbins D. W.; Hartwig J. F. Angew. Chem., Int. Ed. 2013, 52, 933–937. 10.1002/anie.201208203. - DOI - PubMed
    5. Shrestha R.; Mukherjee P.; Tan Y.; Litman Z. C.; Hartwig J. F. J. Am. Chem. Soc. 2013, 135, 8480–8483. 10.1021/ja4032677. - DOI - PubMed
    6. Ricci P.; Krämer K.; Larrosa I. J. Am. Chem. Soc. 2014, 136, 18082–18086. 10.1021/ja510260j. - DOI - PMC - PubMed
    7. Cheng C.; Hartwig J. F. J. Am. Chem. Soc. 2015, 137, 592–595. 10.1021/ja511352u. - DOI - PubMed
    8. Larsen M. A.; Wilson C. V.; Hartwig J. F. J. Am. Chem. Soc. 2015, 137, 8633–8643. 10.1021/jacs.5b04899. - DOI - PubMed
    9. Paudyal M. P.; Adebesin A. M.; Burt S. R.; Ess D. H.; Ma Z.; Kürti L.; Falck J. R. Science 2016, 353, 1144–1147. 10.1126/science.aaf8713. - DOI - PMC - PubMed
    10. Luan Y.-X.; Zhang T.; Yao W.-W.; Lu K.; Kong L.-Y.; Lin Y.-T.; Ye M. J. Am. Chem. Soc. 2017, 139, 1786–1789. 10.1021/jacs.6b12907. - DOI - PubMed
    1. For a general review, see:Engle K. M.; Yu J.-Q. J. Org. Chem. 2013, 78, 8927–8955. 10.1021/jo400159y. - DOI - PMC - PubMed
    1. Zhang Y.-H.; Shi B.-F.; Yu J.-Q. J. Am. Chem. Soc. 2009, 131, 5072–5074. 10.1021/ja900327e. - DOI - PMC - PubMed

LinkOut - more resources