Light-Induced C-H Arylation of (Hetero)arenes by In Situ Generated Diazo Anhydrides
Cantillo, D; Mateos, C; Rincon, JA; de Frutos, O; Kappe, CO
| HERO ID | 3539312 |
|---|---|
| In Press | No |
| Year | 2015 |
| Title | Light-Induced C-H Arylation of (Hetero)arenes by In Situ Generated Diazo Anhydrides |
| Authors | Cantillo, D; Mateos, C; Rincon, JA; de Frutos, O; Kappe, CO |
| Journal | Chemistry: A European Journal |
| Volume | 21 |
| Issue | 37 |
| Page Numbers | 12894-12898 |
| Abstract | Diazo anhydrides (Ar-N=N-O-N=N-Ar) have been known since 1896 but have rarely been used in synthesis. This communication describes the development of a photochemical catalyst-free C-H arylation methodology for the preparation of bi(hetero)aryls by the one-pot reaction of anilines with tert-butyl nitrite and (hetero)arenes under neutral conditions. The key step in this procedure is the in situ formation and subsequent photochemical (>300 nm) homolytic cleavage of a transient diazo anhydride intermediate. The generated aryl radical then efficiently reacts with a (hetero)arene to form the desired bi(hetero)aryls producing only nitrogen, water, and tert-butanol as byproducts. The scope of the reaction for several substituted anilines and (hetero)arenes was investigated. A continuous-flow protocol increasing selectivity and safety has been developed enabling the experimentally straightforward preparation of a variety of substituted bi(hetero)aryls within 45 min of reaction time. |
| Doi | 10.1002/chem.201502357 |
| Pmid | 26239967 |
| Wosid | WOS:000360583000010 |
| Is Certified Translation | No |
| Dupe Override | No |
| Is Public | Yes |
| Language Text | English |