Abstract
A general study on the synthesis of partly bridged octols3a-d and4c-d is described. Tri-bridged diol3c can be prepared in 54% yield in DMSO at 70°C with excess CH2BrCl or in 52% yield in DMF at 70°C with only 4 equiv. of CH2BrCl. 1,3-Di-bridged tetrol4a, one of the two possible di-bridged isomers formed in preference to the other, was obtained in 30% yield. Tri-bridged diols3c andd can be selectively debrominated in one step by treatment with 5 equiv. ofn-BuLi in THF to afford the corresponding dibromo derivatives8a andb in 77% and 76% yields, respectively. After incorporation of the fourth bridge, the remaining two bromines can be replaced by C(O)OMe to give9c (60%), by OH to give9d (62%) or by CN to give9f (>95%). When the lithiated derivatives of3c andd are quenched with electrophiles other thanH +, a selectively functionalized tri-bridged diol with hydroxyl (8c, 47%) and selectively functionalized cavitands with thiomethyl (9g, 25%) or iodo (9h, 20%) groups can be synthesized. Two molecules of9d were coupled with CH2BrCl in DMSO/THF under high dilution conditions to give the flexible hemicarcerand10 in 71% yield.
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This paper is dedicated to the commemorative issue on the 50th anniversary of calixarenes.
Supplementary Data. A list of observed and calculated structure factors have been deposited with the British Document Supply Centre as Supplementary Publication No. SUP 82170 (50 pages)
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Timmerman, P., Boerrigter, H., Verboom, W. et al. Proximally functionalized cavitands and synthesis of a flexible hemicarcerand. J Incl Phenom Macrocycl Chem 19, 167–191 (1994). https://doi.org/10.1007/BF00708981
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DOI: https://doi.org/10.1007/BF00708981