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For the preparation of calix[4]arenes (with one or three substituted bridges) via reaction of diynes with bis(carbene) complexes
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79956067041
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note
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The configuration of the dioxodibromo derivative 4a and its hexabromo precursor 3b was misassigned as cis in ref 2b on the basis of a preliminary crystal structure of 4a (see text).
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35
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3042826692
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Seri, N.; Thondorf, I.; Biali, S. E. J. Org. Chem. 2004, 69, 4774
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79956075382
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note
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Three different partial cone conformations are possible for a proximal disubstituted derivative. These forms differ in the identity of the "unique" ring oriented in the opposite direction to the rest. In this paper, when referring to a partial cone conformation, we refer always to the form in which the ring differing in its orientation to the rest is the one connected to the two carbonyl groups.
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37
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79956142732
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note
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In an attempt to incoporate amino acid moieties into the bridges, a mixture of 3a, l -glutamic acid and TFE was heated to reflux. No incorporation of the amino acid occurred, but the bis(trifluoroethoxy) derivative 10a was obtained in a higher yield than in the absence of the amino acid. This may be related to the acidic nature of the amino acid. The yield shown in eq 1 (82%) refers to the experiment in the presence of l -glutamic acid.
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38
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7244238073
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Hofmann, M.; Hampel, N.; Kanzian, T.; Mayr, H. Angew Chem., Int. Ed. 2004, 43, 5402
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Hofmann, M.1
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39
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79956124565
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Notably, one of the methoxy groups is oriented "in" (toward the central cavity of the macrocycle) in contrast to the usual "out" conformational preference. "In" conformations of methoxy groups have been observed previously in cases where a methoxy group is intramolecularly hydrogen bonded to a hydroxy group attached at a bridge (ref 13b)
-
Notably, one of the methoxy groups is oriented "in" (toward the central cavity of the macrocycle) in contrast to the usual "out" conformational preference. "In" conformations of methoxy groups have been observed previously in cases where a methoxy group is intramolecularly hydrogen bonded to a hydroxy group attached at a bridge (ref 13b).
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40
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0346100550
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A trans -dimesityltetrahydroxycalix[4]arene adopts the 1,2-alternate conformation instead of the cone conformation usually adopted by "classical" tetrahydroxycalix[4]arenes since the cone conformation of the dimesityl derivative is destabilized by the presence of one mesityl group in an axial position
-
A trans -dimesityltetrahydroxycalix[4]arene adopts the 1,2-alternate conformation instead of the cone conformation usually adopted by "classical" tetrahydroxycalix[4]arenes since the cone conformation of the dimesityl derivative is destabilized by the presence of one mesityl group in an axial position. Simaan, S.; Biali, S. E. J. Org. Chem. 2004, 69, 95
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3743064267
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c = π Δ? /?2): Gutowsky, H. S.; Holm, C. H. J. Chem. Phys. 1956, 25, 1228 Since in the case of 18, no coalescence was observed at the highest temperature examined (408 K), the rate calculated by the equation corresponds to a higher limit of the exchange rate at that temperature.
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Gutowsky, H.S.1
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42
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79956081569
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Recently, Wulff and co-workers (ref 12) reported a first example of an optically active methylene-substituted calix[4]arene derivative
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Recently, Wulff and co-workers (ref 12) reported a first example of an optically active methylene-substituted calix[4]arene derivative.
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43
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0006576567
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For an example of O-Me cleavage at a carbocation in a solvolytic process
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For an example of O-Me cleavage at a carbocation in a solvolytic process, see: Rappoport, Z.; Greenblatt, J.; Apeloig, Y. J. Org. Chem. 1979, 44, 3687
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