In order to prepare bridging chiral p-tert-butylcalix[4]crown-5 with a mononitro bridge substituent in a 1,3-alternate conformation, a mononitration method of calix[4]arene bridging methylene has been first developed with tert-butyl nitrite as a nitration reagent. The effects of solvent, reaction temperature, reaction time, and nitration reagent dosage on bridge mononitration have been deeply explored to obtain an optimal nitration condition. The facile nitration presents a new key for calix[4]arene bridge derivatization. After further modification and diastereoisomeric resolution, a pair of bridging chiral p-tert-butylcalix[4]arenes with a monoamino bridge substituent were produced from the bridge-mono-nitrated calix[4]arene. Their preliminary catalysis results in the Henry reaction show good catalytic activities (up to 95% yield) and still low but obviously enhanced enantioselectivities (up to 22.3% ee from 7a, 6% ee from 1), which confirms that the structural transformation indeed improves asymmetric catalysis performances of bridging chiral calix[4]crown-5 amines in a 1,3-alternate conformation.

Bridging chiral p‐tert‐butylcalix[4]arenes (p‐t‐Bu‐BCC's) with different N‐substituted carbamoyl bridge‐substituents (N,N‐dimethylcarbamoyl, N,N‐diethylcarbamoyl and morpholinocarbonyl) were successfully prepared through anionic ortho‐Fries rearrangement from mono‐O‐carbamates of 1,3‐dipropyl‐p‐tert‐butylcalix[4]arene in 65–75% yield. In addition, p‐t‐Bu‐BCC with two N,N‐dimethylcarbamoyl bridge‐substituents was produced by this method from mono‐O‐carbamate of p‐t‐Bu‐BCC with one N,N‐dimethylcarbamoyl bridge‐substituent in 71% yield. However, the synthesis of p‐t‐Bu‐BCC with additional carbamoyl bridge‐substituents using this method could not be attempted, as the required rearrangement precursor failed to be synthesized. Finally, the racemic p‐t‐Bu‐BCC with morpholinocarbonyl bridge‐substituent was optically resolved into a pair of enantiomers, whose absolute configurations were determined through ROESY analysis and ECD comparison.