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
. 2018 Jul 18;9(33):6839-6843.
doi: 10.1039/c8sc02101e. eCollection 2018 Sep 7.

Nickel(0)-catalyzed linear-selective hydroarylation of unactivated alkenes and styrenes with aryl boronic acids

Honggui Lv  1 , Li-Jun Xiao  1 , Dongbing Zhao  1 , Qi-Lin Zhou  1
Affiliations

Nickel(0)-catalyzed linear-selective hydroarylation of unactivated alkenes and styrenes with aryl boronic acids

Honggui Lv et al. Chem Sci. .

Abstract

Herein, we describe the first linear-selective hydroarylation reaction of unactivated alkenes and styrenes with aryl boronic acids, which was achieved by introducing a directing group on the alkenes. This efficient, scalable reaction serves as a method for modular assembly of structurally diverse alkyl arenes, including γ-aryl butyric acid derivatives, which are widely utilized as chemical building blocks for the synthesis of various drugs and other biologically active compounds.

PubMed Disclaimer

Figures

Scheme 1
Scheme 1. Transition-metal-catalyzed hydroarylation of alkenes involving M–H and examples of drugs derived from 4-aryl butyric acids.
Scheme 2
Scheme 2. The reactions of diverse aryl boronic acids 2 with 3-butenoic acid derivative 1a. Yield of isolated product is given. a 5,5-Dimethyl-2-phenyl-1,3,2-dioxaborinane was used as the aryl source. b Triphenylboroxine was used as the aryl source.
Scheme 3
Scheme 3. Reactions of unactivated alkenes with aryl boronic acid 2l. Yield of isolated product is given. a PhPMe2 (10 mol%) as the ligand at 125 °C.
Scheme 4
Scheme 4. Reactions of styrene derivative 1m with aryl boronic acids.
Scheme 5
Scheme 5. Transformations of hydroarylation products 3b and 3s.
Scheme 6
Scheme 6. Control experiment and deuteration experiments.
Scheme 7
Scheme 7. Proposed mechanism of the Ni(0)-catalyzed directing-group-controlled hydroarylation of unactivated alkenes with aryl boronic acids.
See this image and copyright information in PMC

References

    1. For some reviews on metal-hydride chemistry, see:

    2. Rendler S., Oestreich M. Angew. Chem., Int. Ed. 2007;46:498. - PubMed
    3. Deutsch C., Krause N., Lipshutz B. H. Chem. Rev. 2008;108:2916. - PubMed
    4. Pirnot M. T., Wang Y.-M., Buchwald S. L. Angew. Chem., Int. Ed. 2016;55:48. - PMC - PubMed
    5. Greenhalgh M. D., Jones A. S., Thomas S. P. ChemCatChem. 2015;7:190.
    6. Maksymowicz R. M., Bissette A. J., Fletcher S. P. Chem.–Eur. J. 2015;21:5668. - PubMed
    7. Crossley S. W. M., Obradors C., Martinez R. M., Shenvi R. A. Chem. Rev. 2016;116:8912. - PMC - PubMed
    8. Nguyen K. D., Park B. Y., Luong T., Sato H., Garza V. J., Krische M. J. Science. 2016;354:300. - PMC - PubMed

    1. For some reviews on hydroarylation of alkenes, see:

    2. Kakiuchi F., Murai S. Acc. Chem. Res. 2002;35:826. - PubMed
    3. Pan S., Shibata T. ACS Catal. 2013;3:704.
    4. Zeng X. Chem. Rev. 2013;113:6864. - PubMed
    5. Yang L., Huang H. Chem. Rev. 2015;115:3468. - PubMed
    6. Crisenza G. E. M., Bower J. F. Chem. Lett. 2016;45:2.
    7. Dong Z., Ren Z., Thompson S. J., Xu Y., Dong G. Chem. Rev. 2017;117:9333. - PubMed

    1. For some examples on hydroarylation of alkenes using arenes as the aryl source, see:

    2. Sun Z.-M., Zhang J., Manan R. S., Zhao P. J. Am. Chem. Soc. 2010;132:6935. - PubMed
    3. Nakao Y., Yamada Y., Kashihara N., Hiyama T. J. Am. Chem. Soc. 2010;132:13666. - PubMed
    4. Gao K., Yoshikai N. J. Am. Chem. Soc. 2011;133:400. - PubMed
    5. Guan B.-T., Hou Z. J. Am. Chem. Soc. 2011;133:18086. - PubMed
    6. Oyamada J., Hou Z. Angew. Chem., Int. Ed. 2012;51:12828. - PubMed
    7. Pan S., Ryu N., Shibata T. J. Am. Chem. Soc. 2012;134:17474. - PubMed
    8. Lee P.-S., Yoshikai N. Angew. Chem., Int. Ed. 2013;52:1240. - PubMed
    9. Andou T., Saga Y., Komai H., Matsunaga S., Kanai M. Angew. Chem., Int. Ed. 2013;52:3213. - PubMed
    10. Xu W., Yoshikai N. Angew. Chem., Int. Ed. 2014;53:14166. - PubMed
    11. Crisenza G. E. M., McCreanor N. G., Bower J. F. J. Am. Chem. Soc. 2014;136:10258. - PubMed
    12. Bair J. S., Schramm Y., Sergeev A. G., Clot E., Eisenstein O., Hartwig J. F. J. Am. Chem. Soc. 2014;136:13098. - PubMed
    13. Crisenza G. E. M., Sokolova O. O., Bower J. F. Angew. Chem., Int. Ed. 2015;54:14866. - PMC - PubMed
    14. Schramm Y., Takeuchi M., Semba K., Nakao Y., Hartwig J. F. J. Am. Chem. Soc. 2015;137:12215. - PubMed
    15. Ebe Y., Nishimura T. J. Am. Chem. Soc. 2015;137:5899. - PubMed
    16. Filloux C. M., Rovis T. J. Am. Chem. Soc. 2015;137:508. - PMC - PubMed
    17. Hatano M., Ebe Y., Nishimura T., Yorimitsu H. J. Am. Chem. Soc. 2016;138:4010. - PubMed
    18. Kimura N., Kochi T., Kakiuchi F. J. Am. Chem. Soc. 2017;139:14849. - PubMed
    19. Loup J., Zell D., Oliveira J. C. A., Keil H., Stalke D., Ackermann L. Angew. Chem., Int. Ed. 2017;56:14197. - PubMed
    1. Gligorich K. M., Cummings S. A., Sigman M. S. J. Am. Chem. Soc. 2007;129:14193. - PubMed
    2. Iwai Y., Gligorich K. M., Sigman M. S. Angew. Chem., Int. Ed. 2008;47:3219. - PMC - PubMed
    3. Liao L., Sigman M. S. J. Am. Chem. Soc. 2010;132:10209. - PMC - PubMed
    1. Semba K., Ariyama K., Zheng H., Kameyama R., Sakaki S., Nakao Y. Angew. Chem., Int. Ed. 2016;55:6275. - PubMed
    2. Friis S. D., Pirnot M. T., Buchwald S. L. J. Am. Chem. Soc. 2016;138:8372. - PMC - PubMed
    3. Friis S. D., Pirnot M. T., Dupuis L. N., Buchwald S. L. Angew. Chem., Int. Ed. 2017;56:7242. - PMC - PubMed
    4. Lu X., Xiao B., Zhang Z., Gong T., Su W., Yi J., Fu Y., Liu L. Nat. Commun. 2016;7:11129. - PMC - PubMed
    5. Green S. A., Matos J. L. M., Yagi A., Shenvi R. A. J. Am. Chem. Soc. 2016;138:12779. - PubMed
    6. He Y., Cai Y., Zhu S. J. Am. Chem. Soc. 2017;139:1061. - PubMed
    7. Chen F., Chen K., Zhang Y., He Y., Wang Y.-M., Zhu S. J. Am. Chem. Soc. 2017;139:13929. - PubMed
    8. Li W., Boon J. K., Zhao Y. Chem. Sci. 2018;9:600. - PMC - PubMed