Bridging of p-tert-butylthiacalixarene afforded 1,3-dihydroxythiacalixarene-monocrown-5 (3b), 1,2-alternate thiacalixarene-biscrown-4 and -5 (4a,b), and 1,3-alternate thiacalixarene-biscrown-5 and -6 (5a,b), depending on the metal carbonates and oligoethylene glycol ditosylates used. Starting from 1,3-dialkylated thiacalixarenes, the corresponding bridging reaction gave 1,3-alternate, partial-cone, and cone conformers 10-19, depending on the substituents present. Temperature-dependent studies revealed that the conformationally flexible 1,3-dimethoxythiacalixarene-crowns 10a-c exclusively occupy the 1,3-alternate conformation. Demethylation exclusively gave the cone 1,3-dihydroxythiacalixarene-crowns (3a,c), which could not be obtained by direct bridging of thiacalixarene. The different structures were assigned on the basis of several X-ray crystal structures and extensive 2-D 1H NMR studies.
|Number of pages||9|
|Journal||Journal of organic chemistry|
|Publication status||Published - 2004|
van Leeuwen, F. W. B., Beijleveld, H., Kooijman, H., Spek, A. L., Verboom, W., & Reinhoudt, D. (2004). Synthesis and conformational evaluation of p-tert-butylthiacalixarene-crowns. Journal of organic chemistry, 69(11), 3928-3936. https://doi.org/10.1021/jo0401220 S0022-3263(04)00122-7