Catalysis of Intramolecular Morita-Baylis-Hillman and Rauhut-Currier Reactions by Fluorous Phosphines; Facile Recovery by Liquid/Solid Organic/Fluorous Biphase Protocols Involving Precipitation, TeflonTape, and Gore-RastexFiber Academic Article uri icon

abstract

  • The fluorous phosphine P[(CH2)3Rf8] 3 [1, Rf8=(CF2)7CF3; 10 mol%] catalyzes intramolecular Morita-Baylis-Hillman reactions of O=CH-(CH 2)nCH=CH(C=O)R [n/R=2/Ph (2a), 2/S-i-Pr, 3/p-tol] in acetonitrile at 60-72C. Upon cooling, 1 precipitates and is recycled. The products HOCH(CH2)nCH=C(C=O)R are isolated from the supernatant (78-96%). The educt i-PrS(C=O)CH=CH(CH2) 2CH=CH(C=O)S-i-Pr similarly undergoes a Rauhut-Currier reaction to give i-PrS(C=O)CH2CH(CH2)2CH=C(C=O)S-i-Pr (71-73%). In the case of 2a, reactions are also conducted in the presence of Teflon tape or Gore-Rastex fiber. The catalyst now precipitates onto the fluoropolymer support, mechanically facilitating recycling. For each reaction, three to five cycles are conducted. HPLC or GC monitoring of the rates show low activity losses, with Gore-Rastex fiber giving better results than Teflon tape, presumably due to a higher surface area. 2008 Wiley-VCH Verlag GmbH & Co. KGaA.

published proceedings

  • Advanced Synthesis & Catalysis

author list (cited authors)

  • Seidel, F. O., & Gladysz, J. A.

citation count

  • 61

complete list of authors

  • Seidel, Florian O||Gladysz, John A

publication date

  • September 2008

publisher