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Diazomethane umpolung atop anthracene: an electrophilic methylene transfer reagent

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Abstract

Formal addition of diazomethane's terminal nitrogen atom to the 9,10-positions of anthracene yields H2CN2A (1, A = C14H10 or anthracene). The synthesis of this hydrazone is reported from Carpino's hydrazine H2N2A through treatment with paraformaldehyde. Compound 1 has been found to be an easy-to-handle solid that does not exhibit dangerous heat or shock sensitivity. Effective umpolung of the diazomethane unit imbues 1 with electrophilicity at the methylene carbon center. Its reactivity with nucleophiles such as H2CPPh3 and N-heterocyclic carbenes is exploited for C[double bond, length as m-dash]C bond formation with elimination of dinitrogen and anthracene. Similarly, 1 is demonstrated to deliver methylene to a nucleophilic singlet d2 transition metal center, W(ODipp)4 (2), to generate the robust methylidene complex [2[double bond, length as m-dash]CH2]. This behavior is contrasted with that of the Wittig reagent H2CPPh3, a more traditional and Brønsted basic methylene source that upon exposure to 2 contrastingly forms the methylidyne salt [MePPh3][2[triple bond, length as m-dash]CH].

Graphical abstract: Diazomethane umpolung atop anthracene: an electrophilic methylene transfer reagent

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Publication details

The article was received on 17 Oct 2017, accepted on 20 Dec 2017 and first published on 21 Dec 2017


Article type: Edge Article
DOI: 10.1039/C7SC04506A
Citation: Chem. Sci., 2018, Advance Article
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    Diazomethane umpolung atop anthracene: an electrophilic methylene transfer reagent

    M. Joost, W. J. Transue and C. C. Cummins, Chem. Sci., 2018, Advance Article , DOI: 10.1039/C7SC04506A

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