Facile scission of isonitrile carbon-nitrogen triple bond using a diborane(4) reagent.
basic_science · Level V
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- Record sourced from PubMed, PMID 24967910.
- Also identified by DOI 10.1038/ncomms5245 and PMC identifier 4083417.
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Abstract
Transition metal reagents and catalysts are generally effective to cleave all three bonds (one σ and two π) in a triple bond despite its high bonding energy. Recently, chemistry of single-bond cleavage by using main-group element compounds is rapidly being developed in the absence of transition metals. However, the cleavage of a triple bond using non-transition-metal compounds is less explored. Here we report that an unsymmetrical diborane(4) compound could react with carbon monoxide and tert-butyl isonitrile at room temperature. In the latter case, the carbon-nitrogen triple bond was completely cleaved in the absence of transition metal as confirmed by X-ray crystallographic analysis, (13)C NMR spectroscopy with (13)C labelling and DFT calculations. The DFT calculations also revealed the detailed reaction mechanism and indicated that the key for the carbon-nitrogen triple-bond cleavage could be attributed to the presence of nucleophilic nitrogen atom in one of the intermediates.