Scalable Transition-Metal-Free Synthesis of Aryl Amines from Aryl Chlorides through X@RONa-Catalyzed Benzyne Formation.
J Am Chem Soc
; 146(13): 8839-8846, 2024 Apr 03.
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| ID: mdl-38526012
ABSTRACT
Aryl amines are highly useful organic chemicals, but large-scale, transition-metal-free syntheses of aryl amines are surprisingly underdeveloped. A mild and scalable (up to 500 mmol) aryl amine synthesis from benzyne chemistry was invented using easily accessible aryl chlorides as precursors, NaH as a stoichiometric base, and a new type of sodium alkoxide cluster, X@RONa, as a catalyst. The cluster catalyst X@RONa featured an externally hydrophobic dodecameric sodium alkoxide shell housing an encapsulated center anion. The cluster made from methoxy-tert-butanol was found to be the most effective. The intramolecular version of this reaction allowed the synthesis of indolines and indoles. Experimental and computational mechanistic studies revealed that the rate-determining step was likely the transport of solid NaH into the X@RONa cluster in the organic phase.
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J Am Chem Soc
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2024
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Article