| Autor: |
Prusinowski AF; Department of Chemistry and Biochemistry, The Ohio State University, Columbus, Ohio 43210, United States., Twumasi RK; Department of Chemistry and Biochemistry, The Ohio State University, Columbus, Ohio 43210, United States., Wappes EA; Department of Chemistry and Biochemistry, The Ohio State University, Columbus, Ohio 43210, United States., Nagib DA; Department of Chemistry and Biochemistry, The Ohio State University, Columbus, Ohio 43210, United States. |
| Jazyk: |
angličtina |
| Zdroj: |
Journal of the American Chemical Society [J Am Chem Soc] 2020 Mar 18; Vol. 142 (11), pp. 5429-5438. Date of Electronic Publication: 2020 Mar 06. |
| DOI: |
10.1021/jacs.0c01318 |
| Abstrakt: |
A double functionalization of vicinal sp 3 C-H bonds has been developed, wherein a β amine and γ iodide are incorporated onto an aliphatic alcohol in a single operation. This approach is enabled by an imidate radical chaperone, which selectively affords a transient β alkene that is amino-iodinated in situ. Overall, the radical-polar-crossover cascade entails the following key steps: (i) β C-H iodination via 1,5-hydrogen atom transfer (HAT), (ii) desaturation via I 2 complexation, and (iii) vicinal amino-iodination of an in situ generated allyl imidate. The synthetic utility of this double C-H functionalization is illustrated by conversion of aliphatic alcohols to a diverse collection of α,β,γ substituted products bearing heteroatoms on three adjacent carbons. The radical-polar crossover mechanism is supported by various experimental probes, including isotopic labeling, intermediate validation, and kinetic studies. |
| Databáze: |
MEDLINE |
| Externí odkaz: |
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