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Jun 01, 2015;6 (6): 3461-3465.

Generation of 1,2-azaboretidines reduction of ADC borane adducts.

H Braunschweig, A Gackstatter, T Kupfer, T Scheller, F Hupp, A Damme, N Arnold, W C Ewing
Author Information
  1. H Braunschweig: Institut für Anorganische Chemie , Julius-Maximilians-Universität Würzburg , Am Hubland , 97074 Würzburg , Germany . Email: h.braunschweig@uni-wuerzburg.de ; http://www-anorganik.chemie.uni-wuerzburg.de/Braunschweig/.
  2. A Gackstatter: Institut für Anorganische Chemie , Julius-Maximilians-Universität Würzburg , Am Hubland , 97074 Würzburg , Germany . Email: h.braunschweig@uni-wuerzburg.de ; http://www-anorganik.chemie.uni-wuerzburg.de/Braunschweig/.
  3. T Kupfer: Institut für Anorganische Chemie , Julius-Maximilians-Universität Würzburg , Am Hubland , 97074 Würzburg , Germany . Email: h.braunschweig@uni-wuerzburg.de ; http://www-anorganik.chemie.uni-wuerzburg.de/Braunschweig/.
  4. T Scheller: Institut für Anorganische Chemie , Julius-Maximilians-Universität Würzburg , Am Hubland , 97074 Würzburg , Germany . Email: h.braunschweig@uni-wuerzburg.de ; http://www-anorganik.chemie.uni-wuerzburg.de/Braunschweig/.
  5. F Hupp: Institut für Anorganische Chemie , Julius-Maximilians-Universität Würzburg , Am Hubland , 97074 Würzburg , Germany . Email: h.braunschweig@uni-wuerzburg.de ; http://www-anorganik.chemie.uni-wuerzburg.de/Braunschweig/.
  6. A Damme: Institut für Anorganische Chemie , Julius-Maximilians-Universität Würzburg , Am Hubland , 97074 Würzburg , Germany . Email: h.braunschweig@uni-wuerzburg.de ; http://www-anorganik.chemie.uni-wuerzburg.de/Braunschweig/.
  7. N Arnold: Institut für Anorganische Chemie , Julius-Maximilians-Universität Würzburg , Am Hubland , 97074 Würzburg , Germany . Email: h.braunschweig@uni-wuerzburg.de ; http://www-anorganik.chemie.uni-wuerzburg.de/Braunschweig/.
  8. W C Ewing: Institut für Anorganische Chemie , Julius-Maximilians-Universität Würzburg , Am Hubland , 97074 Würzburg , Germany . Email: h.braunschweig@uni-wuerzburg.de ; http://www-anorganik.chemie.uni-wuerzburg.de/Braunschweig/.
PMID: 28706706 DOI: 10.1039/c5sc01077b

Abstract

Reaction of the acyclic (diamino)carbene (ADC) :C(NiPr) () with different dihaloboranes of the type RBX (R = Mes, Dur; X = Cl, Br) smoothly afforded a novel class of ADC-stabilized borane adducts. For MesBBr however, the reaction did not stop at the adduct level, but an uncommon rearrangement process occurred, which eventually resulted in the formation of a 5-membered boracycle after elimination of mesitylene. Chemical reduction of the ADC borane adducts by KC selectively yielded air stable 1,2-azaboretidines. Detailed DFT studies suggest a reduction mechanism involving a highly reactive borylene intermediate, which is converted into the boracycles a rearrangement/C-H activation sequence.

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