Polymers composed of triangular repeating units. Pd2+-catalyzed addition polymerizations of 3,3-dialkylcyclopropenes

Journal of the American Chemical Society

Volumn 118, Issue 48, 1996, Pages 12230-12231

  Rush, Stephen ^a   Reinmuth, Annette ^a   Risse, Wilhelm ^a   O'Brien, John ^b   Ferro, Dino R ^c   Tritto, Incoronata ^c  

^a UNIVERSITY COLLEGE DUBLIN   (Ireland)

^b TRINITY COLLEGE DUBLIN   (Ireland)

^c CNR   (Italy)

Author keywords

[No Author keywords available]

Indexed keywords

CYCLOPROPANE DERIVATIVE; POLYMER;

ARTICLE; NUCLEAR MAGNETIC RESONANCE; POLYMERIZATION; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0030458225     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja961192u     Document Type: Article

References (30)

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13. Synthesis of la,b according to the following: (a) Binger, P. Synthesis 1974, 190.
14. (b) Nesmeyanova, O. A.; Rudashevskaya, T. Y.; Dyachenko, A. I.; Savilova, S. F.; Nesedov, O. M. Synthesis 1982, 296.
15. See Supporting Information for preparative details on the synthesis of le. These threestep syntheses involve the addition of dihalocarbenes to geminally disubstituted olefins, reduction, and elimination of hydrogen halide. They are suitable for monomer preparations on scales of up to several grams. Different monomer syntheses with potential for scale-up are required in order to improve the overall practicality. For other cyclopropene syntheses, see: (c) Closs, G. L.; Closs, L. E.; Böll, W. A. J. Am. Chem. Soc. 1963, 85, 3796.
16. Schleyer, P. v. R.; Williams, J. E.; Blanchard, K. R. J. Am. Chem. Soc. 1970, 92, 2377.
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24. 6] resulted in only a 20% yield of poly-1a indicating that catalyst stability and polymer yields decrease when less bulky and less rigid chelating ligands are used.
25. w(GPC) = 104 000. Cationic [(ligand)Pd(Me)(NCMe)] compounds are potential catalysts for polymers with lower polydispersities. Poly-1a,b (entries 1-6) are only partially soluble at 20 °C in chlorobenzene.
26. This 1,2-cis structure contrasts with the 1,2-trans enchainments of the antifungal agent FR-900848: Barrett, A. G. M.; Kasdorf, K.; Tustin, G. J.; Williams, D. J. J. Chem. Soc., Chem. Commun. 1995, 1143.
27. 13C NMR signals. See Supporting Information for spectroscopic details.
28. 4. See Supporting Information for synthetic and spectroscopic details.
29. 13C NMR signals at δ 30.2 and 16.6 ppm indicating that these signals correspond to meso-units.
30. 13C NMR signals at δ= 30.2, 30.1, 30.0, 29.9, 29.6, and 29.5 (set of signals corresponding to the stereoconfigurations of Me(trans)).