One-Pot Sequences of Reactions with Sol-Gel Entrapped Opposing Reagents: An Enzyme and Metal-Complex Catalysts
- 12 November 2002
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 124 (48) , 14460-14463
- https://doi.org/10.1021/ja020799+
Abstract
We extend our sol-gel methodology of one-pot sequences of reactions with opposing reagents to an enzyme/metal-complex pair. Sol-gel entrapped lipase and sol-gel entrapped RhCl[P(C6H5)3]3 or Rh2Co2(CO)12 were used for one-pot esterification and C−C double bond hydrogenation reactions, leading to saturated esters in good yields. When only the enzyme is entrapped, the homogeneous catalysts quench its activity and poison it. Thus, when 10-undecenoic acid and 1-pentanol were subjected in one pot to the entrapped lipase and to homogeneously dissolved RhCl[P(C6H5)3]3 under hydrogen pressure, only 7% of the saturated 1-pentyl undecanoate was obtained. The yield jumped 6.5-fold when both the enzyme and the catalyst were immobilized separately in silica sol-gel matrixes. Similar one-pot esterifications and hydrogenations by sol-gel entrapped lipase and heterogenized rhodium complexes were carried out successfully with the saturated nonoic, undecanoic, and lauric acids together with several saturated and unsaturated alcohols. The use of (S)-(−)-2-methylbutanol afforded an optically pure ester. The heterogenized lipase is capable of inducing asymmetry during esterification with a prochiral alcohol. Both the entrapped lipase and the immobilized rhodium catalysts can be recovered simply by filtration and recycled in further runs without loss of catalytic activity.Keywords
This publication has 16 references indexed in Scilit:
- Sol−Gel Glass Immunosorbent-Based Determination of s-Triazines in Water and Soil Samples Using Gas Chromatography with a Nitrogen Phosphorus Detection SystemEnvironmental Science & Technology, 2002
- Sol–gel luminescence biosensors: Encapsulation of recombinant E. coli reporters in thick silicate filmsAnalytica Chimica Acta, 2002
- Characterisation of porosity and sensor response times of sol–gel-derived thin films for oxygen sensor applicationsJournal of Non-Crystalline Solids, 2002
- Cyclization and Self-Organization in Polymerization of TrialkoxysilanesMacromolecules, 2001
- Bio-doped Nanocomposite Polymers: Sol−Gel BioencapsulatesChemistry of Materials, 2001
- Sol–gel entrapped Rh2Co2(CO)12: a catalyst precursor for efficient arene hydrogenationJournal of Molecular Catalysis A: Chemical, 2001
- Lipase/Ruthenium-Catalyzed Dynamic Kinetic Resolution of Hydroxy Acids, Diols, and Hydroxy Aldehydes Protected with a Bulky GroupThe Journal of Organic Chemistry, 2001
- One-Pot Reactions with Opposing Reagents: Sol−Gel Entrapped Catalyst and BaseJournal of the American Chemical Society, 2000
- Sol-gel entrapped lipophilic and hydrophilic ruthenium-, rhodium-, and iridium-phosphine complexes as recyclable isomerization catalystsJournal of Molecular Catalysis A: Chemical, 1996
- In situ fixation of lipase-containing hydrophobic sol–gel materials on sintered glass—highly efficient heterogeneous biocatalystsChemical Communications, 1996