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
. 2019 Jun 17;10(30):7246-7250.
doi: 10.1039/c9sc02380a. eCollection 2019 Aug 14.

Palladium-catalyzed enantioselective alkenylation of alkenylbenzene derivatives

Zhi-Min Chen  1 , Jianbo Liu  1 , Jing-Yao Guo  1 , Maximillan Loch  1 , Ryan J DeLuca  1 , Matthew S Sigman  1
Affiliations

Palladium-catalyzed enantioselective alkenylation of alkenylbenzene derivatives

Zhi-Min Chen et al. Chem Sci. .

Abstract

A regioselective and enantioselective palladium-catalyzed relay Heck alkenylation of alkenylbenzene derivatives to construct remote stereocenters is disclosed. Various β-substituted styrenes were readily obtained in moderate yields with good to excellent levels of enantioselectivity. This strategy provides rapid access to enantioenriched δ, ε, ζ, and η-alkenyl aryl compounds from simple starting materials. Mechanistic studies suggest that termination of the relay reaction is controlled by affinity of the arene for the Pd complex during migration.

PubMed Disclaimer

Figures

Scheme 1
Scheme 1. Previous work with carbonyl derivatives and proposed work with alkenylbenzene derivatives.
Fig. 1
Fig. 1. Analysis of side product formation. (A) Reaction scheme. (B) Experimental data. (C) Quantitative analysis. (D) Proposed original of side products.
See this image and copyright information in PMC

References

    1. For selected reviews, see:

    2. Uma R., Crévisy C., Grée R. Chem. Rev. 2003;103:27. - PubMed
    3. Kuznik N., Krompiec S. Coord. Chem. Rev. 2007;251:222.
    4. Krompiec S., Krompiec M., Penczek R., Ignasiak H. Coord. Chem. Rev. 2008;252:1819.
    5. Larionov E., Li H., Mazet C. Chem. Commun. 2014;50:9816. - PubMed
    6. Hassam M., Taher A., Arnott G. E., Green I. R., van Otterlo W. A. L. Chem. Rev. 2015;115:5462. - PubMed
    7. Vilches-Herrera M., Domke L., Börner A. ACS Catal. 2014;4:1706.
    8. Vasseur A., Bruffaerts J., Marek I. Nat. Chem. 2016;8:209. - PubMed
    9. Sommer H., Juliá-Hernández F., Martin R., Marek I. ACS Cent. Sci. 2018;4:153. - PMC - PubMed

    1. Selected examples and reviews on olefin polymerization, see:

    2. Prosenc M.-H., Brintzinger H.-H. Organometallics. 1997;16:3889.
    3. Guan Z., Cotts P. M., McCord E. F., McLain S. J. Science. 1999;283:2059. - PubMed
    4. Ittel S. D., Johnson L. K., Brookhart M. Chem. Rev. 2000;100:1169. - PubMed
    1. Werner E. W., Mei T.-S., Burckle A. J., Sigman M. S. Science. 2012;338:1455. - PMC - PubMed

    1. Selected examples: for Rh-catalyzed chain walking, see ; for Pd-catalyzed chain walking, see ; for Co-catalyzed chain walking, see ; for Ni-catalyzed chain walking, see

    2. Yoshida K., Hayashi T. J. Am. Chem. Soc. 2003;125:2872. - PubMed
    3. Borah A. J., Shi Z. J. Am. Chem. Soc. 2018;140:6062. - PubMed
    4. Oliveira C. C., Angnes R. A., Correia C. R. D. J. Org. Chem. 2013;78:4373. - PubMed
    5. Larionov E., Lin L., Guénée L., Mazet C. J. Am. Chem. Soc. 2014;136:16882. - PubMed
    6. Hamasaki T., Aoyama Y., Kawasaki J., Kakiuchi F., Kochi T. J. Am. Chem. Soc. 2015;137:16163. - PubMed
    7. Singh S., Bruffaerts J., Vasseur A., Marek I. Nat. Commun. 2017;8:14200. - PMC - PubMed
    8. Kohler D. G., Gockel S. N., Kennemur J. L., Waller P. J., Hull K. L. Nat. Chem. 2018;10:333. - PMC - PubMed
    9. Obligacion J. V., Chirik P. J. J. Am. Chem. Soc. 2013;135:19107. - PubMed
    10. Lee W.-C., Wang C.-H., Lin Y.-H., Shih W.-C., Ong T.-G. Org. Lett. 2013;15:5358. - PubMed
    11. He Y., Cai Y., Zhu S. J. Am. Chem. Soc. 2017;139:1061. - PubMed
    12. Juliá-Hernández F., Moragas T., Cornella J., Martin R. Nature. 2017;545:84. - PubMed
    13. Peng L., Li Y., Li Y., Wang W., Pang H., Yin G. ACS Catal. 2018;8:310.
    14. Wang Z., Yin H., Fu G. C. Nature. 2018;563:379. - PMC - PubMed

    1. SelectedSelected examples: examples:

    2. Mei T.-S., Werner E. W., Burckle A. J., Sigman M. S. J. Am. Chem. Soc. 2013;135:6830. - PMC - PubMed
    3. Mei T.-S., Patel H. H., Sigman M. S. Nature. 2014;508:340. - PMC - PubMed
    4. Zhang C., Santiago C. B., Crawford J. M., Sigman M. S. J. Am. Chem. Soc. 2015;137:15668. - PMC - PubMed
    5. Chen Z.-M., Hilton M. J., Sigman M. S. J. Am. Chem. Soc. 2016;138:11461. - PMC - PubMed
    6. Race N. J., Schwalm C. S., Nakamuro T., Sigman M. S. J. Am. Chem. Soc. 2016;138:15881. - PMC - PubMed
    7. Chen Z.-M., Nervig C. S., Deluca R. J., Sigman M. S. Angew. Chem., Int. Ed. 2017;56:6651. - PMC - PubMed
    8. Yuan Q., Sigman M. S. J. Am. Chem. Soc. 2018;140:6527. - PMC - PubMed