Bypassing Ammonia: From N2 to Nitrogen Heterocycles without N1 Intermediates or Transition Metals

Marco Weber; Thomas Kupfer; Merle Arrowsmith; Rian D Dewhurst; Maximilian Rang; Benedikt Ritschel; Sven Titlbach; Martin Ernst; Marieli O Rodrigues; Eufrânio N da Silva Júnior; Holger Braunschweig

doi:10.1002/anie.202402777

Bypassing Ammonia: From N₂ to Nitrogen Heterocycles without N₁ Intermediates or Transition Metals

Angew Chem Int Ed Engl. 2024 May 21;63(21):e202402777. doi: 10.1002/anie.202402777. Epub 2024 Apr 11.

Authors

Marco Weber^{1

2}, Thomas Kupfer^{1

2}, Merle Arrowsmith^{1

2}, Rian D Dewhurst^{1

2}, Maximilian Rang^{1

2}, Benedikt Ritschel^{1

2}, Sven Titlbach³, Martin Ernst³, Marieli O Rodrigues⁴, Eufrânio N da Silva Júnior⁴, Holger Braunschweig^{1

2}

Affiliations

¹ Institute for Inorganic Chemistry, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.
² Institute for Sustainable Chemistry & Catalysis with Boron, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.
³ BASF SE, Carl-Bosch-Straße 38, 67056, Ludwigshafen am Rhein, Germany.
⁴ Department of Chemistry, Institute of Exact Sciences, Federal University of Minas Gerais, UFMG, MG-31270-901, Belo Horizonte, Brazil.

PMID: 38501403
DOI: 10.1002/anie.202402777

Abstract

Diboradiazene compounds, derived in one step from the boron-mediated reduction of dinitrogen (N₂), were treated separately with sulfur and acetic anhydride, providing heterocyclic compounds that are BN isosteres of thiophene and 1,3-oxazole, respectively. These simple reactions represent the final steps in two-step routes to complex heterocycles from N₂ that both circumvent the need for transition metal reagents and completely bypass the traditional intermediate ammonia.

Keywords: boron; main-group chemistry; metallomimetics; nitrogen heterocycles; nitrogen reduction reaction.

Abstract

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