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Issue 10, 2017
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Nucleophilic addition and substitution at coordinatively saturated boron by facile 1,2-hydrogen shuttling onto a carbene donor

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Abstract

The reaction of [(cAACMe)BH3] (cAACMe = 1-(2,6-iPr2C6H3)-3,3,5,5-tetramethylpyrrolidin-2-ylidene) with a range of organolithium compounds led to the exclusive formation of the corresponding (dihydro)organoborates, Li+[(cAACMeH)BH2R] (R = sp3-, sp2-, or sp-hybridised organic substituent), by migration of one boron-bound hydrogen atom to the adjacent carbene carbon of the cAAC ligand. A subsequent deprotonation/salt metathesis reaction with Me3SiCl or spontaneous LiH elimination yielded the neutral cAAC-supported mono(organo)boranes, [(cAACMe)BH2R]. Similarly the reaction of [(cAACMe)BH3] with a neutral donor base L resulted in adduct formation by shuttling one boron-bound hydrogen to the cAAC ligand, to generate [(cAACMeH)BH2L], either irreversibly (L = cAACMe) or reversibly (L = pyridine). Variable-temperature NMR data and DFT calculations on [(cAACMeH)BH2(cAACMe)] show that the hydrogen on the former carbene carbon atom exchanges rapidly with the boron-bound hydrides.

Graphical abstract: Nucleophilic addition and substitution at coordinatively saturated boron by facile 1,2-hydrogen shuttling onto a carbene donor

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Publication details

The article was received on 21 Jul 2017, accepted on 01 Aug 2017 and first published on 04 Aug 2017


Article type: Edge Article
DOI: 10.1039/C7SC03193A
Citation: Chem. Sci., 2017,8, 7066-7071
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    Nucleophilic addition and substitution at coordinatively saturated boron by facile 1,2-hydrogen shuttling onto a carbene donor

    D. Auerhammer, M. Arrowsmith, H. Braunschweig, R. D. Dewhurst, J. O. C. Jiménez-Halla and T. Kupfer, Chem. Sci., 2017, 8, 7066
    DOI: 10.1039/C7SC03193A

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