M-Cyclophanes synthesis

The aryl groups of the styryl systems need not be unsubstituted, as has been illustrated before for the cyclizations encountered in the synthesis of naphthalenophanes from 120. Indeed cyclization to afford a cyclobutane derivative where methoxy groups are on the adjacent ring position to the vinyl moieties has also been studied. The irradiation of 138 affords the m-cyclophanes 139 and 14065. Further study has sought to evaluate the steric effect of o-methoxy groups in such molecules66. 

H. Takemura, M. Kotoku, M. Yasutake, T. Shinmyozu, 9-Fluoro-18-hydroxy-[3.3]meta-cyclophane Synthesis and estimation of a C-F---H-0 hydrogen bond, Eur. J. Org. Chem. 9 (2004) 2019-2024. 

Gabutti S, Schaffner S, Neuburger M, Fischer M, Schafer G, Mayor M (2009) Planar chiral asymmetric naphthalenediimide cyclophanes synthesis, characterization and tunable FRET properties. Org Biomol Chem 7 3222-3229... 

Fig. 2 Examples of Four-component (ABC2) synthesis of m-cyclophanes...

Based on this novel three-component synthesis of 5-aminooxazoles and by designing reaction partners, a two-fold four-component (ABC2) synthesis of m-cyclophane 21 was devised by reacting a diamine (22), a bis-a-isocyanoacetamide... 

When the 1,3-dielectrophile is part of a macrocycle, the cycloaromatization reaction can be used as a synthesis of m-cyclophanes as illustrated in Scheme 49.156... 

In the event, treatment of 622 (X = Br or Cl, Y = Br or I) with 3 equivalents of an aryl Grignard reagent followed by an electrophilic quench gave m-terphenyls 629 in good yield (60-85%). The reaction is not subject to steric hindrance (for example, Ar = 2,6-dimethylphenyl, mesityl, 1-naphthyl or 2-anisyl). It provides a one-pot route to m-terphenyls substituted at the 2 position (or, looked at another way, 2,6-diaryl benzene derivatives), difficult to obtain in other ways. This m-terphenyl synthesis has been used to create two new classes of cyclophanes (cupped- and cappedophanes) . ... 

Yamauchi Y, Fujita M (2010) Self-assembled cage as an endo-template for cyclophane synthesis. Chem Commun 46 5897-5899... 

Okada, Y., Kaneko, M., and Nishimura, J., The formylation of sy -[2.N]metacyclophanes and application to multi-bridged cyclophane synthesis. Tetrahedron Lett., 42, 1919, 2001. 

Okamoto, H., Kimura, M., Satake, K., and Morosawa, S., Synthesis and adiabatic photochemistry of a 1,4-difluorobenzene-naphthalene biplanemer. Bull. Chem. Soc. Jpn., 66, 2436,1993. Nishimura, J., Nakamura, Y., Hayashida, Y., and Kudo, T, Stereocontrol in cyclophane synthesis a photochemical method to overlap aromatic rings, Acc. Chem. Res., 33, 679, 2000. 

Murakami, Y. Functionaiited Cyclophanes as Catalysts and Enzyme Models. 115, 103-151 (1983). Mutter, M., and Pillai, V. N. R. New Perspectives in Polymer-Supported Peptide Synthesis. 106, 119-175 (1982). 

J.-P. Bourgeois, P. Seiler, M. Fibbioli, E. Pretsch, F. Diederich, L. Echegoyen, Cyclophane-Type Fullerene-dibenzo [18] crown-6 Conjugates with trans-1, trans-2, and trans-3 Addition Patterns Regioselective Templated Synthesis, X-ray Crystal Structure, Ionophoric Properties, and Cation-Complexation-Dependent Redox Behavior , Helv. Chim Acta 1999, 82,1572-1595. 

Weber, E., Helbig, C., Seichter, W., Czugler, M., A new functional cyclophane host. Synthesis, complex formation and crystal structures of three inclusion compounds. J. Incl. Phenom. Macrocycl. Chem. 2002, 43, 239-246. 

Chen, G. Y., Lean, J. T., Alcala, M., Mallouk, T. E., Modular synthesis of -acceptor cyclophanes derived from... 

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