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Updated: Nov 2, 2025

Preparation of Contiguous Bisaziridines for Regioselective Ring-Opening Reactions
Published on: July 28, 2022
Diverse ring-opening reactions of rhodium η4-azaborete complexes
Merlin Heß1, Tom E Stennett1, Felipe Fantuzzi1
1Institute for Inorganic Chemistry and Institute for Sustainable Chemistry & Catalysis with Boron, Julius-Maximilians-Universität Würzburg Am Hubland 97074 Würzburg Germany h.braunschweig@uni-wuerzburg.de.
Abstract:
Sequential treatment of [Rh(COE)2Cl]2 (COE = cyclooctene) with PiPr3, alkyne derivatives and BuN[triple bond, length as m-dash]BMes (Mes = 2,4,6-trimethylphenyl) provided functionalized rhodium η4-1,2-azaborete complexes of the form (η4-azaborete)RhCl(PiPr3). The scope of this reaction was expanded to encompass alkynes with hydrogen, alkyl, aryl, ferrocenyl, alkynyl, azaborinyl and boronate ester substituents. Treatment of these complexes with PMe3 led to insertion of the rhodium atom into the B-C bond of the BNC2 ring, forming 1-rhoda-3,2-azaboroles. Addition of N-heterocyclic carbenes to azaborete complexes led to highly unusual rearrangements to rhodium η2,κ1-allenylborylamino complexes via deprotonation and C-N bond cleavage. Heating and photolysis of an azaborete complex also led to rupture of the C-N bond followed by subsequent rearrangements, yielding an η4-aminoborylallene complex and two isomeric η4-butadiene complexes.
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