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
. 2011 Nov 30;133(47):19020-3.
doi: 10.1021/ja209235d. Epub 2011 Nov 8.

Nickel-catalyzed Heck-type reactions of benzyl chlorides and simple olefins

Ryosuke Matsubara  1 , Alicia C Gutierrez, Timothy F Jamison
Affiliations

Nickel-catalyzed Heck-type reactions of benzyl chlorides and simple olefins

Ryosuke Matsubara et al. J Am Chem Soc. .

Abstract

Nickel-catalyzed intermolecular benzylation and heterobenzylation of unactivated alkenes to provide functionalized allylbenzene derivatives are described. A wide range of both the benzyl chloride and alkene coupling partners are tolerated. In contrast to analogous palladium-catalyzed variants of this process, all reactions described herein employ electronically unbiased aliphatic olefins (including ethylene), proceed at room temperature, and provide 1,1-disubstituted olefins over the more commonly observed 1,2-disubstituted olefins with very high selectivity.

PubMed Disclaimer

Figures

Figure 1
Figure 1
Substrates that did not undergo the desired benzylation.
Scheme 1
Scheme 1. Proposed Catalytic Cycle and ORTEP Drawing of η3-Nickel Complex 14a
a P= PR3.
See this image and copyright information in PMC

References

    1. Heck RF. J. Am. Chem. Soc. 1968;90:5518.
    2. Mizoroki T, Mori K, Ozaki A. Bull. Chem. Soc. Jpn. 1971;44:581.

    1. For reviews on the Heck-Mizoroki reaction, see: Bräse S, de Meijere A. In: Metal-catalyzed Cross-coupling Reactions. Diederich F, Stang PJ, editors. Weinheim; Wiley-VCH: 1998. Chapter 3. Link JT, Overman LE. In: Metal-catalyzed Cross-coupling Reactions. Diederich F, Stang PJ, editors. Weinheim; Wiley-VCH: 1998. Chapter 6. Brseä S, de Meijere A. In: Metal-catalyzed Cross-coupling Reactions. 2nd ed. de Meijere A, Diederich F, editors. Weinheim; Wiley-VCH: 2004. Chapter 5. Beletskaya IP, Cheprakov AV. Chem. Rev. 2000;100:3009. Dounay AB, Overman LE. Chem. Rev. 2003;103:2945–2963. Oes-treich M. Top. Organomet. Chem. 2007;24:169–192. Shibasaki M, Ohshima T, Itano W. Science of Synthesis. 2011;3:483–512. Le Bras J, Muzart J. Chem. Rev. 2011;111:1170–1214.

    1. In the context of this publication, “benzylation” refers to reaction at the carbon attached to an aromatic ring.

    1. Heck RF, Nolley JP., Jr. J. Org. Chem. 1972;37:2320.
    1. Wu G.-z., Lamaty F, Negishi E.-i. J. Org. Chem. 1989;54:2507.
    2. Yi P, Zhuangyu Z, Hongwen H. Synth. Commun. 1992;22:2019.
    3. Yi P, Zhuangyu Z, Hongwen H. Synthesis. 1995;245
    4. Kumar P. Org. Prep. Proc. Int. 1997;29:477.
    5. Wang L, Pan Y, Jiang X, Hu H. Tetrahedron Lett. 2000;41:725.
    6. Narahashi H, Yamamoto A, Shimizu I. Chem. Lett. 2004;33:348.
    7. Narahashi H, Shimizu I, Yamamoto A. J. Organomet. Chem. 2008;693:283.

Publication types