| Autor: |
Moerdyk JP; Department of Chemistry and Biochemistry, The University of Texas at Austin , Austin, Texas 78712, United States., Blake GA, Chase DT, Bielawski CW |
| Jazyk: |
angličtina |
| Zdroj: |
Journal of the American Chemical Society [J Am Chem Soc] 2013 Dec 18; Vol. 135 (50), pp. 18798-801. Date of Electronic Publication: 2013 Dec 04. |
| DOI: |
10.1021/ja411467p |
| Abstrakt: |
An N,N'-diamidocarbene (DAC) was found to activate a broad range of primary as well as secondary aliphatic and aromatic amines. The relative rates measured for the insertion of the DAC into the primary amines were consistent with an electrophilic activation mechanism; in contrast, the DAC functioned as a nucleophile upon treatment with secondary aryl amines. Collectively, these results constituted the first ambiphilic process for an isolable carbene. By comparison, an analogous diaminocarbene was found to serve exclusively as a nucleophile under similar conditions and led to the discovery of the first organic reagent to reversibly activate ammonia. |
| Databáze: |
MEDLINE |
| Externí odkaz: |
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