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Bis-calixarenes are prepared by the oxidative coupling of monophenolic precursors. Due to the lack of substituents ortho- to the biaryl linkage, these hosts are conformationally flexible. Crystal structures exhibiting biaryl torsion angles of 35° and 0° have been reported: (a) P. Neri, A. Bottino, F. Cunsolo, M. Piattelli, E. Gavuzzo, Angew. Chem. Int. Ed. 1998, 37, 166. doi:10.1002/(SICI)1521-3773(19980202)37:1/2<166::AID-ANIE166> 3.0.CO;2-P
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note; (doi:10.1021/JA984182X) failed to give any detectable biaryl product
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Attempts to carry out Ullmann couplings of the monobromide analogue of 1 under a variety of conditions (Cu bronze, DMF, reflux; Cu bronze, NMP, reflux; Cu bronze, 2,6-diethylaniline, 250°C, cf. A. P. Degnan, A. I. Meyers, J. Am. Chem. Soc. 1999, 121, 2762 (doi:10.1021/JA984182X) failed to give any detectable biaryl product.
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Lipshutz's procedures (ref. [12]) describe the use of CuCN then TMEDA/oxygen at -125 or -78°C. Reported modifications of this procedure include the use of CuCn · 2LiBr then 1,3-dinitrobenzene at -40°C: D. R. Spring, S. Krishnan, S. L. Schreiber, J. Am. Chem. Soc. 2000, 122, 5656. doi:10.1021/JA0010507
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Previous examples of solid-state EtOH·bowl caviplexes: (a) I. Higler, H. Boerrigter, W. Verboom, H. Kooijman, A. L. Spek, D. N. Reinhoudt, Eur. J. Org. Chem. 1998, 1597. doi:10.1002/(SICI)1099-0690(199808)1998:8<1597::AID-EJOC1597>3.0.CO;2-1
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These energy minimizations were carried out as follows: A model of dimer 8 was constructed from X-ray coordinates of the tetrabromocavitand bowl 1 and feet were removed. Energy minimizations were performed from an initial conformation with a ca. 90° biaryl. Calculations were performed using MacSpartan 1.0.4 (Wavefunction Inc.: Irvine, CA).
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