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. 2020 May 3;2020(16):2362-2368.
doi: 10.1002/ejoc.201901600. Epub 2019 Nov 21.

Recent Advances in Radical Addition to Alkenylboron Compounds

Gabriel J Lovinger  1 , James P Morken  1
Affiliations

Recent Advances in Radical Addition to Alkenylboron Compounds

Gabriel J Lovinger et al. European J Org Chem. .

Abstract

The addition of carbon-centered radicals to alkenylboron compounds provides a useful method for the construction of organoboron reagents which are versatile reagents in chemical synthesis. While the first examples of this type or process appeared 70 years ago, until recently, attention to this type of reaction has been limited. A number of examples of this reactivity have been demonstrated recently, and strategies are emerging that allow for tuning the reagent structure in order to modulate reactivity. This review surveys recent advances in this class of reaction.

Keywords: Addition Reactions; Carbon Radicals; Catalysis; Organoboron; Stereocontrol.

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Figures

Scheme 1.
Scheme 1.
Matteson’s atom transfer radical addition (1959).
Scheme 2.
Scheme 2.
Walton and Carboni’s calculated energies of H-transfer reactions.
Scheme 3.
Scheme 3.
Frontier orbital interactions in radical additions to alkenylboron compounds.
Scheme 4.
Scheme 4.
Carboni’s polarity-matched radical addition.
Scheme 5.
Scheme 5.
Zard’s polarity-matched xanthate radical addition reactions.
Scheme 6.
Scheme 6.
Aggarwal’s photoredox-catalyzed radical addition of carboxylic acids to alkenylboron reagents. Conditions: RCO2H, 1% Ir catayst, 1.1 equiv Cs2CO3, DMF, 35 °C, 40 W blue LED.
Scheme 7.
Scheme 7.
Aggarwal’s photoredox-catalyzed radical addition of carboxylic acids to alkenylboron reagents. Conditions: RCO2H, 1% Ir catayst, 1.1 equiv Cs2CO3, DMF, 35 °C, 40 W blue LED.
Scheme 8.
Scheme 8.
Baran’s hydrogen-atom-transfer/radical conjugate addition involving alkenylboron compounds.
Scheme 9.
Scheme 9.
Morken’s sequential radical addition/cross-coupling with vinylB(pin).
Scheme 10.
Scheme 10.
Sheikh and Leonori’s photocatalytic radical vinylation with alkenyltrifluoroborates.
Scheme 11.
Scheme 11.
Radical-polar cross-over reactions of alkenylboron “ate’ complexes and organic halides.
Scheme 12.
Scheme 12.
Generalized reaction mechanism for the radical addition/metallate shift involving alkenylboron derived “ate” complexes.
Scheme 13.
Scheme 13.
Stereospecificity in radical-polar crossover couplings, and Studer's approach to the synthesis of allylic boronates.
Scheme 14.
Scheme 14.
Yuan and Shi's geminal diboron synthesis by radical addition to B2(pin)2 derived “ate” complexes.
Scheme 15.
Scheme 15.
Aggarwal's radical addition/metallate shift involving strained bicyclic boronate complexes.
See this image and copyright information in PMC

References

    1. Review:

    2. Sanford C, Aggarwal VK, Chem. Commun 2017, 53, 5481–5494. - PubMed
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