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Asymmetric Addition of Boron and Silicon Nucleophiles

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Book cover Progress in Enantioselective Cu(I)-catalyzed Formation of Stereogenic Centers

Part of the book series: Topics in Organometallic Chemistry ((TOPORGAN,volume 58))

Abstract

The recent progress in catalytic asymmetric carbon–boron and carbon–silicon bond formation catalyzed by chiral copper(I) complexes is tremendous. Within less than a decade, the majority of fundamental bond-forming reactions in this arena, that is, conjugate addition, 1,2-addition and allylic substitution, were accomplished. These enantioselective transformations had been either elusive or not even known before. This chapter summarizes these fascinating developments together with a brief mechanistic discussion as these copper(I) catalyses share transmetalation of interelement bonds such as B–B and Si–B as a common feature.

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Notes

  1. 1.

    For an analysis of the stereochemical outcome using phosphine-type ligands, see [20].

  2. 2.

    For related relevant work, see: α,β-unsaturated ketimines/NHC–copper(I) catalysts [21], α,β-unsaturated imines/phosphoramidite–copper(I) catalyst [22], in situ-formed α,β-unsaturated aldimines/phosphine–copper(I) catalysts [23], and α,β-unsaturated esters/NHC–copper(I) catalysts [24, 25].

  3. 3.

    For the 1,4-addition to α,β-unsaturated sulfones, see [27].

  4. 4.

    For a metal-free protocol using a chiral phosphine as catalyst, see [47].

  5. 5.

    For a racemic version with chirality transfer from an enantiopure starting material, see [53].

  6. 6.

    For the use of related NHC–copper(I) complex L7∙CuCl in the enantioselective 1,4-addition of nucleophilic boron, see Sect. 2.1, Scheme 7 [29].

  7. 7.

    For copper(I)-catalyzed addition of nucleophilic boron across C–C triple bonds, see [74–78]. For copper(I)-catalyzed addition of nucleophilic silicon across C–C triple bonds, see [79–85].

  8. 8.

    The group of Hall used enantiopure β,β-diboron-substituted esters in stereospecific and chemoselective Suzuki–Miyaura cross-coupling reactions (not shown) [91].

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Acknowledgments

M.O. thanks the Einstein Foundation (Berlin) for an endowed professorship.

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  1. Institut für Chemie, Technische Universität Berlin, Straße des 17. Juni 115, 10623, Berlin, Germany

    Alexander Hensel & Martin Oestreich

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  1. Alexander Hensel
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  2. Martin Oestreich
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Correspondence to Martin Oestreich .

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  1. Stratingh Institute for Chemistry, University of Groningen, Groningen, The Netherlands

    Syuzanna R. Harutyunyan

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Hensel, A., Oestreich, M. (2015). Asymmetric Addition of Boron and Silicon Nucleophiles. In: Harutyunyan, S. (eds) Progress in Enantioselective Cu(I)-catalyzed Formation of Stereogenic Centers. Topics in Organometallic Chemistry, vol 58. Springer, Cham. https://doi.org/10.1007/3418_2015_156

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