Oxidative Amidation of Nitroalkanes with Amine Nucleophiles using Molecular Oxygen and Iodine.
The formation of amides and peptides often necessitates powerful yet mild reagent systems. The reagents used, however, are often expensive and highly elaborate. New atom-economical and practical methods that achieve such goals are highly desirable. Ideally, the methods should start with substrates that are readily available in both chiral and non-chiral forms and utilize cheap reagents that are compatible with a wide variety of functional groups, steric encumberance, and epimerizable stereocenters. A direct oxidative method was developed to form amide and peptide bonds between amines and primary nitroalkanes simply by using I2 and K2 CO3 under O2 . Contrary to expectations, a 1:1 halogen-bonded complex forms between the iodonium source and the amine, which reacts with nitronates to form α-iodo nitroalkanes as precursors to the amides.
Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki-Aza, Aoba-ku, Sendai 980-8578 (Japan) http://www.ykbsc.chem.tohoku.ac.jp.
Jing
J
Li
Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki-Aza, Aoba-ku, Sendai 980-8578 (Japan) http://www.ykbsc.chem.tohoku.ac.jp.|Present address: School of Chemistry, University of Lincoln, Brayford Pool, Lincoln LN6 7TS (UK).
Martin J
MJ
Lear
Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki-Aza, Aoba-ku, Sendai 980-8578 (Japan) http://www.ykbsc.chem.tohoku.ac.jp.
Yuya
Y
Kawamoto
Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki-Aza, Aoba-ku, Sendai 980-8578 (Japan) http://www.ykbsc.chem.tohoku.ac.jp.
Shigenobu
S
Umemiya
Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki-Aza, Aoba-ku, Sendai 980-8578 (Japan) http://www.ykbsc.chem.tohoku.ac.jp.
Alice R
AR
Wong
Research and Analytical Center for Giant Molecules, Graduate School of Science, Tohoku University, Sendai 980-8578 (Japan).
Eunsang
E
Kwon
Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki-Aza, Aoba-ku, Sendai 980-8578 (Japan) http://www.ykbsc.chem.tohoku.ac.jp.|Present address: Faculty of Science, Ibaraki University, Ibaraki 310-8512 (Japan).
Itaru
I
Sato
Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki-Aza, Aoba-ku, Sendai 980-8578 (Japan) http://www.ykbsc.chem.tohoku.ac.jp. yhayashi@m.tohoku.ac.jp.
Yujiro
Y
Hayashi
D000473:Alkanes / Q000737:chemistry*; D000577:Amides / Q000138:chemical synthesis* / Q000737:chemistry; D000588:Amines / Q000737:chemistry*; D007455:Iodine / Q000737:chemistry*; D015394:Molecular Structure; D009574:Nitro Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*
D000473:Alkanes; D000577:Amides; D000588:Amines; D009574:Nitro Compounds; D007455:Iodine; D010100:Oxygen
amidation; halogen bonding; iodination; peptide formation; umpolung