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  Mechanistic Insights into the Kinetic and Regiochemical Control of the Thiol-Promoted Catalytic Synthesis of Diphenolic Acid

van de Vyver, S., Helsen, S., Geboers, J., Yu, F., Thomas, J., Smet, M., et al. (2012). Mechanistic Insights into the Kinetic and Regiochemical Control of the Thiol-Promoted Catalytic Synthesis of Diphenolic Acid. ACS Catalysis, 2(12), 2700-2704. doi:10.1021/cs300635r.

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van de Vyver, Stijn1, Author
Helsen, Sasja1, Author
Geboers, Jan1, 2, Author              
Yu , Feng1, Author
Thomas, Joice1, Author
Smet, Mario1, Author
Dehaen, Wim1, Author
Roman-Leshkov, Yuriy3, Author
Hermans, Ive4, Author
Sels, Bert1, Author
Affiliations:
1Katholieke Univ Leuven, B-3001 Louvain, Belgium, ou_persistent22              
2Research Department Schüth, Max-Planck-Institut für Kohlenforschung, Max Planck Society, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr, DE, ou_1445589              
3MIT, Dept Chem Engn, Cambridge, MA 02139 USA, ou_persistent22              
4ETH, Dept Chem & Appl Biosci, CH-8093 Zurich, Switzerland , ou_persistent22              

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 Abstract: The mechanism of the acid-catalyzed condensation between levulinic acid and phenol to form diphenolic acid (DPA) was investigated using a combination of sulfonated hyperbranched poly(arylene oxindole)s and thiols. Taft-type steric and electronic parameters were applied to study the correlation between the nature of the thiols and the condensation rate. The kinetic effect of thiols to tune the regiochemical control was shown to be dependent on the substituent size of the thiols. Although thiols cause an increase in the regioselectivity to the desired p,p'-DPA, the isomer distribution is found to converge to a thermodynamic equilibrium at high conversions of levulinic acid. The hitherto unconsidered acid-catalyzed isomerization of p,p'-DPA to o,p'-DPA was demonstrated by condensation reactions with both m-cresol and C-13-labeled phenol supported by density functional theory (DFT) calculations.

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 Dates: 2012-12-01
 Publication Status: Published in print
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 Rev. Type: Peer
 Identifiers: DOI: 10.1021/cs300635r
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Title: ACS Catalysis
Source Genre: Journal
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Pages: - Volume / Issue: 2 (12) Sequence Number: - Start / End Page: 2700 - 2704 Identifier: -