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  • Review Article
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Stereoselectivity in Pd-catalysed cross-coupling reactions of enantioenriched nucleophiles

Nature Reviews Chemistry volume 4, pages 584–599 (2020)Cite this article

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Abstract

Advances in Pd-catalysed cross-coupling reactions have facilitated the development of stereospecific variants enabling the use of configurationally stable, enantioenriched, main-group organometallic nucleophiles to form C(sp3)–C(sp2) bonds. Such stereospecific cross-coupling reactions constitute a powerful synthetic approach to attaining precise 3D control of molecular structure, allowing new stereogenic centres to be readily introduced into molecular architectures. Examples of stereospecific, Pd-catalysed cross-coupling reactions have been reported for isolable enantioenriched alkylboron, alkyltin, alkylgermanium and alkylsilicon nucleophiles. In these reactions, a single, dominant stereospecific pathway of transmetallation to palladium is required to effect efficient chirality transfer to the cross-coupled product. However, the potential for competing stereoretentive and stereoinvertive pathways of transmetallation complicates the stereochemical transfer in these processes and impedes the rational development of new stereospecific cross-coupling variants. In this Review, we describe the use of enantioenriched organometallic nucleophiles in stereospecific, Pd-catalysed cross-coupling reactions. We focus on systems involving well-defined, isolable, enantioenriched nucleophiles in which a clear stereochemical course of transmetallation is followed. Specific modes of electronic activation that influence the reactivity of alkylmetal nucleophiles are described and presented in the context of their impact on the stereochemical course of cross-coupling reactions. We expect that this Review will serve as a valuable resource to assist in deconvoluting the many considerations that potentially impact the stereochemical outcome of Pd-catalysed cross-coupling reactions.

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Fig. 1: Stereochemical considerations in the coupling of enantioenriched nucleophiles.
Fig. 2: Use of unactivated, stereodefined organoboron nucleophiles in Pd-catalysed cross-coupling reactions.
Fig. 3
Fig. 4: Propargylic and allylic organoboron nucleophiles in couplings.
Fig. 5: Suzuki couplings of activated alkylboron nucleophiles that occur with net inversion of stereochemistry.
Fig. 6: Examples of the coupling of enantioenriched organostannanes in copper-promoted palladium-catalysed Stille reactions.
Fig. 7: Copper-catalysed and copper-mediated cross-couplings of alkylstannanes.
Fig. 8: Pd-catalysed cross-coupling reactions of enantioenriched alkyltin, alkylgermanium and alkylsilicon nucleophiles.

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Acknowledgements

The authors thank the City College of New York, the National Institutes of Health (R01GM131079) and the National Science Foundation (CHE-1665189) for support of this work.

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  1. Department of Chemistry and Biochemistry, The City College of New York, New York, NY, USA

    Xinghua Ma, Benjamin Murray & Mark R. Biscoe

  2. Ph.D. Program in Chemistry, The Graduate Center of The City University of New York, New York, NY, USA

    Xinghua Ma, Benjamin Murray & Mark R. Biscoe

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Ma, X., Murray, B. & Biscoe, M.R. Stereoselectivity in Pd-catalysed cross-coupling reactions of enantioenriched nucleophiles. Nat Rev Chem 4, 584–599 (2020). https://doi.org/10.1038/s41570-020-00222-9

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