Easy access to nucleophilic boron through diborane to magnesium boryl metathesis

Research output: Contribution to journalArticle

25 Citations (Scopus)

Abstract

Organoboranes are some of the most synthetically valuable and widely used intermediates in organic and pharmaceutical chemistry. Their synthesis, however, is limited by the behaviour of common boron starting materials as archetypal Lewis acids such that common routes to organoboranes rely on the reactivity of boron as an electrophile. While the realization of convenient sources of nucleophilic boryl anions would open up a wealth of opportunity for the development of new routes to organoboranes, the synthesis of current candidates is generally limited by a need for highly reducing reaction conditions. Here, we report a simple synthesis of a magnesium boryl through the heterolytic activation of the B-B bond of bis(pinacolato)diboron, which is achieved by treatment of an easily generated magnesium diboranate complex with 4-dimethylaminopyridine. The magnesium boryl is shown to act as an unambiguous nucleophile through its reactions with iodomethane, benzophenone and N,N′-di-isopropyl carbodiimide and by density functional theory.

LanguageEnglish
Article number15022
Pages1-7
Number of pages7
JournalNature Communications
Volume8
Early online date7 Apr 2017
DOIs
StatusPublished - 7 Apr 2017

Fingerprint

diborane
Boron
metathesis
Magnesium
magnesium
boron
synthesis
routes
Organic Chemistry
Carbodiimides
organic chemistry
Lewis Acids
Nucleophiles
Pharmaceutical Chemistry
nucleophiles
Density functional theory
Anions
reactivity
Chemical activation
activation

ASJC Scopus subject areas

  • Chemistry(all)
  • Biochemistry, Genetics and Molecular Biology(all)
  • Physics and Astronomy(all)

Cite this

Easy access to nucleophilic boron through diborane to magnesium boryl metathesis. / Pécharman, Anne Frédérique; Colebatch, Annie L.; Hill, Michael S.; McMullin, Claire L.; Mahon, Mary F.; Weetman, Catherine.

In: Nature Communications, Vol. 8, 15022, 07.04.2017, p. 1-7.

Research output: Contribution to journalArticle

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AU - Mahon, Mary F.

AU - Weetman, Catherine

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AB - Organoboranes are some of the most synthetically valuable and widely used intermediates in organic and pharmaceutical chemistry. Their synthesis, however, is limited by the behaviour of common boron starting materials as archetypal Lewis acids such that common routes to organoboranes rely on the reactivity of boron as an electrophile. While the realization of convenient sources of nucleophilic boryl anions would open up a wealth of opportunity for the development of new routes to organoboranes, the synthesis of current candidates is generally limited by a need for highly reducing reaction conditions. Here, we report a simple synthesis of a magnesium boryl through the heterolytic activation of the B-B bond of bis(pinacolato)diboron, which is achieved by treatment of an easily generated magnesium diboranate complex with 4-dimethylaminopyridine. The magnesium boryl is shown to act as an unambiguous nucleophile through its reactions with iodomethane, benzophenone and N,N′-di-isopropyl carbodiimide and by density functional theory.

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