Diazomethane umpolung atop anthracene: An electrophilic methylene transfer reagent
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c7sc04506a.pdf
Description
Published version
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491.03 KB
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Author(s)
Joost, Maximilian
Transue, Wesley J.
Cummins, Christopher C.
Date Issued
December 2017
Journal
Chemical Science
Publisher
Royal Society of Chemistry (RSC)
Citation
Joost, Maximilian, et al. “Diazomethane Umpolung atop Anthracene: An Electrophilic Methylene Transfer Reagent.” Chemical Science 9, 6 (2018): 1540–43. © 2018 The Royal Society of Chemistry
Version
Final published version
Abstract
Formal addition of diazomethane's terminal nitrogen atom to the 9,10-positions of anthracene yields H[subscript 2]CN[subscript 2]A (1, A = C[subscript 14]H[subscript 10] or anthracene). The synthesis of this hydrazone is reported from Carpino's hydrazine H[subscript 2]N[subscript 2]A 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 H[subscript 2]CPPh[subscript 3] 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 d[superscript 2] transition metal center, W(ODipp)[subscript 4] (2), to generate the robust methylidene complex [2=CH[subscript 2]]. This behavior is contrasted with that of the Wittig reagent H[subscript 2]CPPh[subscript 3], a more traditional and Brønsted basic methylene source that upon exposure to 2 contrastingly forms the methylidyne salt [MePPh[subscript 3]][2≡CH].]
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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Creative Commons Attribution 3.0 unported license
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DOI of Published Version
https://doi.org/10.1039/C7SC04506A
