Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 22, Issue 16, Pages 5538-5542Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201600540
Keywords
amides; iodine; peroxides; radicals; umpolung
Categories
Funding
- Grants-in-Aid for Scientific Research [16K13942] Funding Source: KAKEN
Ask authors/readers for more resources
Recently, we developed a direct method to oxidatively convert primary nitroalkanes into amides that entailed mixing an iodonium source with an amine, base, and oxygen. Herein, we systematically investigated the mechanism and likely intermediates of such methods. We conclude that an amine-iodonium complex first forms through N-halogen bonding. This complex reacts with aci-nitronates to give both -iodo- and ,-diiodonitroalkanes, which can act as alternative sources of electrophilic iodine and also generate an extra equimolar amount of I+ under O-2. In particular, evidence supports ,-diiodonitroalkane intermediates reacting with molecular oxygen to form a peroxy adduct; alternatively, these tetrahedral intermediates rearrange anaerobically to form a cleavable nitrite ester. In either case, activated esters are proposed to form that eventually reacts with nucleophilic amines in a traditional fashion.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available