Arylene ethynylene macrocycles prepared by precipitation-driven alkyne metathesis

Journal of the American Chemical Society

Volumn 126, Issue 40, 2004, Pages 12796-

  Zhang, Wei ^a   Moore, Jeffrey S ^a  

^a UNIVERSITY OF ILLINOIS AT URBANA CHAMPAIGN   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKYNE; MACROCYCLIC COMPOUND;

ARTICLE; CHEMICAL REACTION; CHEMICAL STRUCTURE; CONCENTRATION (PARAMETERS); POLYMERIZATION; PRECIPITATION; REACTION ANALYSIS; RING CLOSING METATHESIS; ROOM TEMPERATURE; SYNTHESIS;

EID: 5644250509     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja046531v     Document Type: Article

References (11)

1. (a) Höger, S. Chem. Eur. J. 2004, 10, 1320-1329.
2. (b) Zhao, D.; Moore, J. S. Chem. Commun. 2003, 807-818.
3. (c) Yamaguchi, Y.; Yoshida, Z. Chem. Eur. J. 2003, 9, 5430-5440.
4. (d) Bunz, U. H. F.; Rubin, Y.; Tobe, Y. Chem. Soc. Rev. 1999, 28, 107-119.
5. Rowan, S. J.; Cantrill, S. J.; Cousins, G. R. L.; Sanders, J. K. M.; Stoddart, J. F. Angew. Chem., Int. Ed. 2002, 41, 898-952.
6. Bunz previously reported the synthesis of macrocycles via alkyne metathesis. Under their conditions, which required high temperature (150 °C), the desired products were only obtained in 0.5-6% yields. Ge, P.-H.; Fu, W.; Herrmann, W. A.; Herdtweck, E.; Campana, C.; Adams, R. D.; Bunz, U. H. F. Angew. Chem., Int. Ed. 2000, 39, 3607-3610.
7. (a) Zhang, W.; Kraft, S.; Moore, J. S. Chem. Commun. 2003, 832-833.
8. (b) Zhang, W.; Kraft, S.; Moore, J. S. J. Am. Chem. Soc. 2004, 126, 329-335.
9. A small amount of pentameric macrocycle is present in the isolated macrocyclic product. For the large-scale synthesis of 2e, the macrocyclic product was a 9:1 hexacycle/pentacycle mixture. The pentacycle could be separated from the hexacycle by column chromatography.
10. 4; 10 mol % catalyst.
11. Preliminary studies have shown the reversibility of macrocycle formation in the case of 2e and 2f. The macrocyclic products appear to be thermodynamically favored over larger macrocycles and open-chain oligomer and polymer, analogous to the molecular architectures prepared via coordination reactions. See: Leininger, S.; Olenyuk, B.; Stang, P. J. Chem. Rev. 2000, 100, 853-908.