Structure elucidation of the intermediate in triethylborane-mediated radical addition of oxime ethers with 2D- and 3D-DOSY NMR.
The structures of the components in the triethylborane-mediated radical addition reaction of oxime ether were investigated by 1H- and 3D-DOSY NMR methods. It has been impossible to physically separate the unstable intermediates; therefore, the structures were thus far unidentified. It has been possible to elucidate the structures of these unstable intermediates using Diffusion-Ordered Spectroscopy (DOSY) methods for the reaction in an NMR tube. The DOSY methods resolved the spectra of each starting compound, intermediate and product having different diffusion coefficients. The structure of the intermediate was shown to be due to the bonding of diethylborane to the nitrogen atom of the alkoxyamino group.
Nakakoshi
Masamichi
M
Chemical Analysis Center, Yokohama National University, 79-5 Tokiwadai, Hodogaya-ku, Yokohama, 240-8501, Japan. m-nakako@ynu.ac.jp
Ueda
Masafumi
M
Sakurai
Satoshi
S
Miyata
Okiko
O
Sugiura
Makiko
M
Naito
Takeaki
T
D001880:Boranes / Q000737:chemistry*; D001896:Boron Compounds / Q000737:chemistry*; D004058:Diffusion; D004987:Ethers / Q000737:chemistry; D006898:Hydroxylamines / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy / Q000379:methods*; D015394:Molecular Structure; D009584:Nitrogen / Q000032:analysis; D010091:Oximes / Q000737:chemistry*
D001880:Boranes; D001896:Boron Compounds; D004987:Ethers; D006898:Hydroxylamines; C522233:N-n-propyl-N-benzylhydroxylamine; D010091:Oximes; D009584:Nitrogen; C079756:triethylborane