Nickel-Catalyzed Cross-Coupling of Ammonia or Primary Alkylamines with (Hetero)aryl Sulfamates, Carbamates, or Pivalates

Abstract

A catalyst system capable of effecting the cross-coupling of ammonia or primary alkylamines with (hetero)aryl sulfamates, carbamates, or pivalates is reported for the first time. The air-stable nickel(II) pre-catalyst C1 tolerates a broad spectrum of heterocyclic functionality within both reaction partners, as well as ether, nitrile, pyrrole, trifluoromethyl, and boronate ester substituents. In the case of reactions involving primary alkylamines and (hetero)aryl sulfamates and carbamates, room-temperature cross-couplings were achieved.

Key words

nickel - sulfamates - carbamates - pivalates - C–N cross-coupling - ammonia - primary alkylamines

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• 16 Procedure for Catalyst Screening In a nitrogen-filled glovebox, Ni(COD)₂ (3.3 mg, 0.012 mmol, 0.1 equiv), ligand (0.012 mmol, 0.1 equiv), 1a (29.2 mg, 0.12 mmol, 1.0 equiv), NaOt-Bu (25.4 mg, 0.26 mmol, 2.2 equiv), and NH₃ (0.5 M solution in 1,4-dioxane, 0.96 mL, 0.48 mmol, 4 equiv) were added to a screw-capped glass vial containing a magnetic stir bar. The vial was sealed with a cap containing a PTFE septum, removed from the glovebox, and placed in a temperature-controlled aluminum heating block set to 80 °C, at which point magnetic stirring was initiated. After 24 h, calibrated GC analysis of reaction aliquots was used to estimate the consumption of 1a and percentage of product (2a) formed. Pre-catalyst screening was conducted by using an identical protocol, where C1–C3 (0.1 equiv) were individually used in place of added Ni(COD)₂ and ligand. Procedures for Scope of Cross-Coupling Using C1 Ammonia In a nitrogen-filled glovebox, pre-catalyst C1 (5–7.5 mol%), (hetero)aryl pseudohalide (1.0 equiv), base (2.2 equiv), and NH₃ (0.5 M solution in 1,4-dioxane, 0.96 mL, 0.48 mmol, 4 equiv) were added to a screw-capped vial containing a magnetic stir bar. The vial was sealed with a cap containing a PTFE septum, removed from the glovebox, and placed in a temperature-controlled aluminum heating block set to 80 °C, at which point magnetic stirring was initiated. After 16 h, the vial was then removed from the heating block and was allowed to cool to ambient temperature. The crude product was purified by flash-column chromatography to afford the purified product. Primary Alkylamines A protocol analogous to that employed in ammonia monoarylation was employed, using C1 (5–10 mol%), base (2.2 or 6.0 equiv, as specified), primary alkylamine (1.1 equiv), and solvent (toluene or 1,4-dioxane, as specified), with reactions conducted at 25 °C or 110 °C (as specified).
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• 19 Concurrent with this work, Schranck, Tlili and co-workers reported a nickel-catalyzed coupling of aryl carbamates with ammonia: Schranck J. Furer P. Hartmann V. Tlili A. Eur. J. Org. Chem. 2017; 3496