Diazomethane umpolung atop anthracene: an electrophilic methylene transfer reagent

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 CC 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 [2CH₂]. 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][2CH].