METACYCLOPHANES AND RELATED-COMPOUNDS .26. TETRAHYDROXY[2.N.2.N]METACYCLOPHANES - PREPARATION, REACTIONS, AND SPECTRA

Tetra-terf-butyltetrahydroxy- and tetrahydroxy[2.n.2.ra]metacyclophanes, 1 and 2 (a, n = 1; b, n = 2; and c, n = 3), were prepared from p-tert-butylanisole by using the tert-butyl group as a positional protective function. Acetylation of lb and 2b with Ac20 gave tetraacetates 9 and 10. Methylation of 2b with Mel gave tetramethoxy 11, while dimethoxy derivatives 12 and 13 were obtained in the reaction of lb and 2b, respectively, with CH2N2. Tetrakis(allyloxy)MCPs, 14 and 15 were prepared by the reaction of lb and 2b, respectively, with allyl bromide. When heated in diethylaniline, 14 was deallylated, giving lb, while 15 afforded the Claisen rearrangement product 16. Bromination of 2b gave tetrabromoMCP 17. Oxidation of 2b gave the expected tetrakis quinone 19, which, on reduction with Zn in the presence of Ac20, afforded octaacetate 20. Of these tetranuclear MCPs, tetra-hydroxy[2.2.2.2]MCPs lb, 2b, 16, and 17 form the strong intramolecular hydrogen bond, while the corresponding [2.1.2.1]MCPs la and 2a and [2.3.2.3]MCPs lc and 2c do not. © 1990, American Chemical Society. All rights reserved.