Hemisphere-shaped calixarenes and their analogs: synthesis, structure, and chiral recognition ability

作者：Sawada Tsuyoshi^*; Hongo Takuya; Matsuo Nami; Konishi Masakazu; Kawaguchi Tsutomu; Ihara Hirotaka

来源：Tetrahedron, 2011, 67(25): 4716-4722.

DOI：10.1016/j.tet.2011.04.025

• Calixarene
• Metacyclophane
• Pinacol rearrangement

The hemisphere-shaped calixarene la and its split-hemisphere-shaped isomer 1b were synthesized from [2.1.2.1]metacyclophane (MCP) 3 by pinacol rearrangement and subsequent intramolecular acetalization. Their structures were revealed by X-ray crystallography and H-1 NMR spectroscopy. The temperature-dependence of the intramolecular acetalization to provide la and 1b was examined. The results indicated that la is the dominant product at high temperatures, and the values of AN and AS were estimated to be -18.3 +/- 0.37 kJ mol(-1), -59.1 +/- 1.12 kJ mol(-1) K-1, respectively. The dinitro derivative 7 and tetranitro derivatives 8 were obtained by ipso-nitration at the upper rims of la. The optical resolution and chiral recognition ability of racemic mixture 7 were investigated by HPLC systems.

• 出版日期2011-6-24