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Coupling dinitrogen and hydrocarbons through aryl migration.

ABSTRACT: The activation of abundant molecules such as hydrocarbons and atmospheric nitrogen (N₂) remains a challenge because these molecules are often inert. The formation of carbon-nitrogen bonds from N₂ typically has required reactive organic precursors that are incompatible with the reducing conditions that promote N₂ reactivity¹, which has prevented catalysis. Here we report a diketiminate-supported iron system that sequentially activates benzene and N₂ to form aniline derivatives. The key to this coupling reaction is the partial silylation of a reduced iron-dinitrogen complex, followed by migration of a benzene-derived aryl group to the nitrogen. Further reduction releases N₂-derived aniline, and the resulting iron species can re-enter the cyclic pathway. Specifically, we show that an easily prepared diketiminate iron bromide complex² mediates the one-pot conversion of several petroleum-derived arenes into the corresponding silylated aniline derivatives, by using a mixture of sodium powder, crown ether, trimethylsilyl bromide and N₂ as the nitrogen source. Numerous compounds along the cyclic pathway are isolated and crystallographically characterized, and their reactivity supports a mechanism for sequential hydrocarbon activation and N₂ functionalization. This strategy couples nitrogen atoms from N₂ with abundant hydrocarbons, and maps a route towards future catalytic systems.

SUBMITTER: McWilliams SF

PROVIDER: S-EPMC7430000 | biostudies-literature | 2020 Aug

REPOSITORIES: biostudies-literature

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Coupling dinitrogen and hydrocarbons through aryl migration.

McWilliams Sean F SF Broere Daniël L J DLJ Halliday Connor J V CJV Bhutto Samuel M SM Mercado Brandon Q BQ Holland Patrick L PL

Nature 20200812 7820

The activation of abundant molecules such as hydrocarbons and atmospheric nitrogen (N2) remains a challenge because these molecules are often inert. The formation of carbon-nitrogen bonds from N2 typically has required reactive organic precursors that are incompatible with the reducing conditions that promote N2 reactivity1, which has prevented catalysis. Here we report a diketiminate-supported iron system that sequentially activates benzene and N ...[more]

PMID: 32788733

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Project description:The advent of transition-metal catalysed strategies for forming new carbon-carbon bonds has revolutionized the field of organic chemistry, enabling the efficient synthesis of ligands, materials, and biologically active molecules. In cases where a single metal fails to promote a selective or efficient transformation, the synergistic cooperation of two distinct catalysts--multimetallic catalysis--can be used instead. Many important reactions rely on multimetallic catalysis, such as the Wacker oxidation of olefins and the Sonogashira coupling of alkynes with aryl halides, but this approach has largely been limited to the use of metals with distinct reactivities, with only one metal catalyst undergoing oxidative addition. Here, we demonstrate that cooperativity between two group 10 metal catalysts--(bipyridine)nickel and (1,3-bis(diphenylphosphino)propane)palladium--enables a general cross-Ullmann reaction (the cross-coupling of two different aryl electrophiles). Our method couples aryl bromides with aryl triflates directly, eliminating the use of arylmetal reagents and avoiding the challenge of differentiating between multiple carbon-hydrogen bonds that is required for direct arylation methods. Selectivity can be achieved without an excess of either substrate and originates from the orthogonal reactivity of the two catalysts and the relative stability of the two arylmetal intermediates. While (1,3-bis(diphenylphosphino)propane)palladium reacts preferentially with aryl triflates to afford a persistent intermediate, (bipyridine)nickel reacts preferentially with aryl bromides to form a transient, reactive intermediate. Although each catalyst forms less than 5 per cent cross-coupled product in isolation, together they are able to achieve a yield of up to 94 per cent. Our results reveal a new method for the synthesis of biaryls, heteroaryls, and dienes, as well as a general mechanism for the selective transfer of ligands between two metal catalysts. We anticipate that this reaction will simplify the synthesis of pharmaceuticals, many of which are currently made with pre-formed organometallic reagents, and lead to the discovery of new multimetallic reactions.

Dataset Information

Coupling dinitrogen and hydrocarbons through aryl migration.

Publications

Coupling dinitrogen and hydrocarbons through aryl migration.

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