Mononitration of a Calix[4]arene Methylene Bridge: Synthesis and Preliminary Catalysis Performances of Bridging Chiral p-tert-Butylcalix[4]arenes with a Monoamino Bridge Substituent in a 1,3-Alternate Conformation

• Published in: Journal of organic chemistry Vol. 86; no. 5; pp. 3952 - 3959
• Main Authors: Peng, Xin-Bang, He, Di, Sun, Guan-Nan, Yu, Yu, Ma, Ying-Hong, Tang, Sheng-An, Dong, Wei-Li, Li, Shao-Yong
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 05.03.2021; Amer Chemical Soc
• Subjects: Chemistry; Chemistry, Organic; Physical Sciences; Science & Technology
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/acs.joc.0c02795

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.