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. 2019 Oct 9;10(45):10601-10606.
doi: 10.1039/c9sc04122b. eCollection 2019 Dec 7.

Cu-catalyzed C-C bond formation of vinylidene cyclopropanes with carbon nucleophiles

Jichao Chen  1 , Shang Gao  1 , Ming Chen  1
Affiliations

Cu-catalyzed C-C bond formation of vinylidene cyclopropanes with carbon nucleophiles

Jichao Chen et al. Chem Sci. .

Erratum in

Abstract

The development of Cu-catalyzed addition of carbon nucleophiles to vinylidene cyclopropanes was reported. The reactions with 1,1-bisborylmethane provided homopropargylic boronate products by forming a C-C bond at the terminal carbon atom of the allene moiety of vinylidene cyclopropanes. Alkynyl boronates are also suitable nucleophile precursors in reactions with vinylidene cyclopropanes, and skipped diynes were obtained in high yields. In addition, the Cu-enolate generated from the initial addition of nucleophilic copper species to vinylidene cyclopropanes can be intercepted by an external electrophile. As such, vinylidene cyclopropane serves as a linchpin to connect a nucleophile and an electrophile by forming two carbon-carbon bonds sequentially.

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Figures

Scheme 1
Scheme 1. Potential competing pathways for Cu-catalyzed reactions with vinylidene cyclopropane.
Scheme 2
Scheme 2. Proposed synthesis of skipped diynes from Cu-catalyzed alkyne addition to vinylidene cyclopropanes.
Scheme 3
Scheme 3. Three-component reaction of vinylidene cyclopropanes, Cu-nucleophiles and electrophiles. Reaction conditions: vinylidene cyclopropane 1 (0.1 mmol, 1 equiv.), CuCl (10 mol%), 1,1-bisborylmethane 2 or alkynyl boronate 4e (0.11 mmol, 1.1 equiv.), NaOtBu (0.11 mmol, 1.1 equiv.), electrophile (2 equiv.), THF (0.5 mL). Yields of isolated products are listed.
Scheme 4
Scheme 4. Transformation of the reaction products.
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References

    1. For selected reviews on vinylidene cyclopropanes, see:

    2. Maeda H., Mizuno K. J. Synth. Org. Chem., Jpn. 2004;62:1014.
    3. Shi M., Shao L.-X., Lu J.-M., Wei Y., Mizuno K., Maeda H. Chem. Rev. 2010;110:5883. - PubMed
    4. Yang S., Shi M. Acc. Chem. Res. 2018;51:1667. - PubMed
    1. Campbell M. J., Pohlhaus P. D., Min G., Ohmatsu K., Johnson J. S. J. Am. Chem. Soc. 2008;130:9180. - PubMed

    1. For selected recent references with vinylidene cyclopropanes, see:

    2. Yang S., Rui K.-H., Tang X.-Y., Xu Q., Shi M. J. Am. Chem. Soc. 2017;139:5957. - PubMed
    3. Ji C., Xu Q., Shi M. Adv. Synth. Catal. 2017;359:974.
    4. Yuan W., Dong X., Shi M., McDowell P., Li G. Org. Lett. 2012;14:5582. - PMC - PubMed
    5. Wu L., Shi M. Chem.–Eur. J. 2011;17:13160. - PubMed
    6. Wu L., Shi M. Eur. J. Org. Chem. 2011;2011:1099.
    7. Wu L., Shi M. Chem.–Eur. J. 2010;16:1149. - PubMed
    8. Wu L., Shi M. J. Org. Chem. 2010;75:2296. - PubMed

    1. For selected recent reviews:

    2. Semba K., Fujihara T., Terao J., Tsuji Y. Tetrahedron. 2015;71:2183.
    3. Pulis A. P., Yeung K., Procter D. J. Chem. Sci. 2017;8:5240. - PMC - PubMed

    1. For selected recent references on Cu-catalyzed reactions of allene with boron nucleophiles, see:

    2. Semba K., Fujihara T., Terao J., Tsuji Y. Angew. Chem., Int. Ed. 2013;52:12400. - PubMed
    3. Semba K., Shinomiya M., Fujihara T., Terao J., Tsuji Y. Chem.–Eur. J. 2013;19:7125. - PubMed
    4. Yuan W., Zhang X., Yu Y., Ma S. Chem.–Eur. J. 2013;19:7193. - PubMed
    5. Meng F., McGrath K. P., Hoveyda A. H. Nature. 2014;513:367. - PMC - PubMed
    6. Semba K., Bessho N., Fujihara T., Terao J., Tsuji Y. Angew. Chem., Int. Ed. 2014;53:9007. - PubMed
    7. Meng F., Li X., Torker S., Shi Y., Shen X., Hoveyda A. H. Nature. 2016;537:387. - PMC - PubMed
    8. Zhao W., Montgomery J. J. Am. Chem. Soc. 2016;138:9763. - PubMed
    9. Zhao J., Szabó K. J. Angew. Chem., Int. Ed. 2016;55:1502. - PMC - PubMed
    10. Yeung K., Ruscoe R. E., Rae J., Pulis A. P., Procter D. J. Angew. Chem., Int. Ed. 2016;55:11912. - PMC - PubMed
    11. Huang Y., Torker S., Li X., del Pozo J., Hoveyda A. H. Angew. Chem., Int. Ed. 2019;58:2685. - PMC - PubMed