PMID: 11929253Apr 4, 2002Paper

The boron-catalyzed polymerization of dimethylsulfoxonium methylide. A living polymethylene synthesis

Journal of the American Chemical Society
B. B. BuschHuide Zhu

Abstract

Trialkyl and aryl organoboranes catalyze the polymerization of dimethylsulfoxonium methylide (1). The product of the polymerization is a tris-polymethylene organoborane. Oxidation affords linear telechelic alpha-hydroxy polymethylene. The polymer molecular weight was found to be directly proportional to the stoichiometric ratio of ylide/borane, and polydispersities as low as 1.01-1.03 have been realized. Although oligomeric polymethylene has been the most frequent synthetic target of this method, polymeric star organoboranes with molecular weights of 1.5 million have been produced. The average turnover frequency at 120 degrees C in 1,2,4,5-tetrachlorobenzene/toluene is estimated at >6 x 10(6) g of polymethylene (mol boron)(-1) h(-1). The mechanism of the polyhomologation reaction involves initial formation of a zwitterionic organoborane.ylide complex which breaks down in a rate-limiting 1,2-alkyl group migration with concomitant expulsion of a molecule of DMSO. The reaction was found to be first order in the borane catalyst and zero order in ylide. DMSO does not interfere with the reaction. The temperature dependence of the reaction rate yielded the following activation energy parameters (toluene, DeltaH(++) = 23.2 kcal/mol, De...Continue Reading

References

Oct 24, 2001·The Journal of Organic Chemistry·K. J. SheaB. B. Busch
Dec 26, 2001·Chemical Reviews·S D IttelM Brookhart
Dec 26, 2001·Chemical Reviews·K Matyjaszewski, J Xia
Oct 1, 1996·Journal of the American Society for Mass Spectrometry·W J EvansJ Greaves
Feb 15, 1999·Angewandte Chemie·George J P BritovsekDuncan F Wass

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Citations

Apr 3, 2010·Journal of the American Chemical Society·Juan C TuberquiaG Kane Jennings
Apr 23, 2004·Organic Letters·Masahito OchiaiNobuyuki Higashiura
Nov 4, 2009·Chemical Communications : Chem Comm·Cathleen M CruddenChristopher J Lata
Mar 27, 2004·Chemical Communications : Chem Comm·Jonathan M Stoddard, Kenneth J Shea
Jan 10, 2017·Chemical Communications : Chem Comm·De Wang, Nikos Hadjichristidis
Apr 27, 2010·Chemical Society Reviews·Erica JellemaBas de Bruin
Jan 21, 2014·Macromolecular Rapid Communications·Hefeng ZhangNikos Hadjichristidis
Aug 27, 2019·Angewandte Chemie·Viko LadeltaNikos Hadjichristidis
Aug 22, 2013·Chemical Communications : Chem Comm·Hefeng ZhangNikos Hadjichristidis
Nov 8, 2007·Journal of the American Chemical Society·Guang Y FangVarinder K Aggarwal
Sep 10, 2010·Accounts of Chemical Research·Jun Luo, Kenneth J Shea
Oct 2, 2003·Journal of the American Chemical Society·Carl E WagnerKenneth J Shea
Nov 19, 2021·Journal of the American Chemical Society·Feng LiHarm-Anton Klok

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