Insights into the Origins of Configurational Stability of Axially Chiral Biaryl Amines with an Intramolecular N−H−N Hydrogen Bond
- Kazuhiro Hayashi ,
- Nobuyuki Matubayasi ,
- Changsheng Jiang ,
- Tomoyuki Yoshimura ,
- Swapan Majumdar ,
- Takahiro Sasamori ,
- Norihiro Tokitoh , and
- Takeo Kawabata
Abstract
Configurationally stable chiral biaryl amines with an intramolecular N−H−N hydrogen bond have been developed. The barriers for racemization are in the range of 19.3−28.2 kcal/mol, which corresponds to the half-lives of racemization of the enantiomers in the range of 7 s to 2 years at 20 °C. Enantiomers of some of these compounds were separable by HPLC with chiral stationary phases. The biaryl amines are supposed to have a conformation similar to that of a binaphthyl skeleton, which was indicated by an X-ray crystal analysis of a biaryl amine. The N-H appears at 11.1−13.3 ppm in their 1H NMR spectrum in CDCl3, indicating strong hydrogen bonding. Biaryl amines with an extremely strong intramolecular N−H−N hydrogen bond (δNH ∼13 ppm) were assumed to undergo racemization without cleavage of an N−H−N hydrogen bond, while those with a mediumly strong N−H−N hydrogen bond (δNH ∼11 ppm) are assumed to undergo racemization via cleavage of an N−H−N hydrogen bond. Hydrogen/deuterium exchange of a chiral biaryl amine was found to proceed without any trace of racemization.
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