Mechanism of oxidative amidation of nitroalkanes with oxygen and amine nucleophiles using electrophilic iodine

Li, Jing and Lear, Martin and Kwon, Eunsang and Hayashi, Yujiro (2016) Mechanism of oxidative amidation of nitroalkanes with oxygen and amine nucleophiles using electrophilic iodine. Chemistry - A European Journal, 22 (16). pp. 5538-5542. ISSN 0947-6539

Documents
Chem_Eur_J_2016_accepted.pdf

Request a copy
SI-To be published.pdf
[img]
[Download]
22298 chem 201600540_MJL_edit.pdf
Proof

Request a copy
[img] PDF
Chem_Eur_J_2016_accepted.pdf - Whole Document
Restricted to Repository staff only

1MB
[img]
Preview
PDF
SI-To be published.pdf - Supplemental Material

1MB
[img] PDF
22298 chem 201600540_MJL_edit.pdf - Whole Document
Restricted to Repository staff only

445kB
Item Type:Article
Item Status:Live Archive

Abstract

Recently, we developed a direct way to oxidatively convert primary nitroalkanes into amides. This entailed mixing an iodonium source with an amine, a base, and oxygen. Herein, we systematically investigated the mechanism and likely intermediates. We conclude that an amine-iodonium complex first forms through N-halogen bonding. This complex reacts with aci-nitronates to give both alpha-iodo and alpha-,alpha-diiodo nitroalkanes. These iodinated species can act as alternative sources of electrophilic iodine and also generate an extra equimolar amount of “I+” under O2. In particular, evidence supports alpha-,alpha-diiodo nitroalkanes reacting with molecular oxygen to form a peroxy adduct; alternatively, these tetrahedral intermediates rearrange anaerobically into a cleavable nitrite ester. In either case, activated esters are proposed form, which eventually react with nucleophilic amines in a traditional fashion.

Additional Information:This work was supported by a Grant-in-Aid for Scientific Research on Innovative Areas “Advanced Molecular Transformations by Organocatalysts” from The Ministry of Education, Culture, Sports, Science and Technology, Japan, and the Multidimensional Materials Science Leaders Program (to M.J.L.).
Keywords:Peptides, Amidation, Methodology, JCNotOpen
Subjects:F Physical Sciences > F160 Organic Chemistry
Divisions:College of Science > School of Chemistry
Related URLs:
ID Code:22298
Deposited On:26 Feb 2016 16:01

Repository Staff Only: item control page