Synlett 2003(2): 0199-0202
DOI: 10.1055/s-2003-36803
LETTER
© Georg Thieme Verlag Stuttgart · New York

Synthesis and Characterization of Chiral Calixarene Analogs Locked in the Cone Conformation by the Photocycloaddition

Yukihiro Okada, Masashi Yoshida, Jun Nishimura*
Department of Chemistry, Gunma University, Kiryu 376-8515, Japan
e-Mail: okada@chem.gunma-u.ac.jp;
Further Information

Publication History

Received 17 October 2002
Publication Date:
22 January 2003 (online)

Abstract

A bisphenol derivative was used as the starting material. [2+2] Photocycloaddition of tetraolefin gave the desired calix[4]arene analogs having chiral and achiral structure in 12-77% yields. The optical resolution was successfully achieved by using the HPLC method. The calixarene analog formed a 1:1 complex with alkali metal ions and extracted large metal picrates better than small ones.

11

Compd.: MS (M+): 1H NMR δ (intensity, multiplicity, J in Hz). 5c: Calcd for C42H46O6: 646: 2.16-2.62 (8 H, m), 3.17 (2 H, d, 15), 3.52 (2 H, m), 3.58-3.70 (6 H, m), 3.75 (6 H, s), 3.77-3.83 (4 H, m), 4.13 (2 H, m), 4.22 (2 H, d, 15), 4.43 (2 H, m), 5.94 (2 H, dd, 1.8, 8.0), 6.17 (2 H, dd, 1.8, 8.0), 6.32 (2 H, t, 8.0), 7.07 (2 H, dd, 1.8, 8.0), 7.16 (2 H, t, 8.0), 7.38 (2 H, dd, 1.8, 8.0). 6c: Calcd for C42H46O6: 646: 2.24-2.58 (8 H, m), 3.17 (2 H, d, 15), 3.26 (6 H, s), 3.50-3.95 (12 H, m), 4.21 (2 H, d, 15), 4.16 (2 H, m), 4.60 (2 H, m), 6.44 (2 H, dd, 2.0, 7.8), 6.67 (2 H, dd, 2.0, 7.8), 6.69 (2 H, t, 7.8), 6.76 (2 H, dd, 2.0, 7.8), 6.81 (2 H, t, 7.8), 6.86 (2 H, dd, 2.0, 7.8). 5d: Calcd for C44H50O7: 690: 2.24-2.52 (8 H, m), 3.13 (2 H, d, 15), 3.63 (6 H, s), 3.64-4.06 (16 H, m), 4.16 (2 H, d, 15), 4.26 (2 H, m), 4.36 (2 H, m), 6.40 (2 H, dd, 1.8, 7.5), 6.56 (2 H, dd, 1.8, 7.5), 6.63 (2 H, t, 7.5), 6.67 (2 H, dd, 1.8 & 7.5), 6.86 (2 H, t, 7.5), 6.98 (2 H, dd, 1.8, 7.5). 6d: Calcd for C44H50O7: 690: 2.26-2.50 (8 H, m), 3.17 (2 H, d, 15), 3.20 (6 H, s), 3.58-3.94 (16 H, m), 4.26 (2 H, d, 15), 4.28 (2 H, m), 4.44 (2 H, m), 6.52 (2 H, dd, 1.8, 7.5), 6.66 (2 H, dd, 1.8, 7.5), 6.72 (2 H, dd, 1.8, 7.8), 6.76 (2 H, t, 7.5), 6.78 (2 H, dd, 1.8, 7.5), 6.83 (2 H, dd, 1.8, 7.5).