期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 22, 期 16, 页码 5538-5542出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201600540
关键词
amides; iodine; peroxides; radicals; umpolung
资金
- Grants-in-Aid for Scientific Research [16K13942] Funding Source: KAKEN
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.
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