Center for Molecular Modeling - S. Cottenie

Insight in the activity and diastereoselectivity of various Lewis acid catalysts for the citronellal cyclization

mat — Wed, 13 Feb 2013 12:38:41 +0000

M. Vandichel, F. Vermoortele, S. Cottenie, D. De Vos, M. Waroquier, V. Van Speybroeck

Journal of Catalysis

305, 118-129

2013

Abstract

Industrial (-)-menthol production generally relies on the hydrogenation of (-)-isopulegol, which is in turn produced with high selectivity by cyclization of (+)-citronellal. This paper uses a combined theoretical and experimental approach to study the activity and selectivity of three Lewis acid catalysts for this reaction, namely ZnBr2, aluminum tris(2,6-diphenylphenoxide) (ATPH) and the heterogeneous metal-organic framework Cu3BTC2 (BTC = benzene-1,3,5-tricarboxylate). ATPH is a strong Lewis acid homogeneous catalyst with bulky ligands which provides very high selectivities for the desired stereo-isomer (> 99 %). The performance of the catalysts was evaluated as a function of temperature, which revealed that higher catalyst activity allows working at lower temperatures and improves the selectivity for isopulegol. The selectivity distribution is kinetically driven for ZnBr2 and ATPH. The theoretical selectivity distributions rely on the determination of an extensive set of diastereomeric transition states, for which the differences in free energy have been calculated using a complementary set of ab initio techniques. Given the sensitivity of the selectivity to small Gibbs free energy differences, the agreement between experimental and theoretical selectivities is satisfactory. On basis of the obtained insights rational design of new catalysts may be obtained. As proof of concept, the hypothetical Cu3(BTC-(NO2)3)2 Lewis catalyst – in which each phenyl hydrogen of the BTC ligand is replaced by a nitro group - is predicted to be very selective.

Open Access version available at UGent repository

DOI

http://dx.doi.org/10.1016/j.jcat.2013.04.017

Private attachment

Vandichel-JC-2013-ActivitySelectivityLewisAcidCatalystsForCitronellalCyclization.pdf

13_jcatlysis_305_118_vandichel.pdf

NCCC-XII

wim — Thu, 07 Feb 2013 13:54:44 +0000

Noordwijkerhout, The Netherlands

Monday, 28 February, 2011 to Wednesday, 2 March, 2011

Participant(s)

K. Hemelsoet, M. Vandichel, T. Bogaerts, J. Van der Mynsbrugge, S. Cottenie, K. De Wispelaere, J. De Ridder, B. De Sterck

Project ref.

FWO mandaat, BOF mandaat

Conference reference

NCCC-XII

Modeling Lewis acid catalyzed reactions in MOFs: How to solve the challenges?

mat — Tue, 07 Aug 2012 08:01:54 +0000

M. Vandichel, F. Vermoortele, B. Van de Voorde, S. Cottenie, D. De Vos, M. Waroquier, V. Van Speybroeck

p. 37

Talk

Conference / event / venue

MOF2012

Edinburgh, UK

Sunday, 16 September, 2012 to Wednesday, 19 September, 2012

Abstract (private)

4183.pdf

Conference reference

MOF2012

Selectivity prediction: making the comparison between extended cluster and periodic calculations

wim — Mon, 02 Jul 2012 14:09:43 +0000

M. Vandichel, F. Vermoortele, S. Cottenie, D. De Vos, M. Waroquier, V. Van Speybroeck

p. 122-123

Poster

Conference / event / venue

ICAMM 2012 & VASP Workshop

Nantes, France

Monday, 11 June, 2012 to Friday, 15 June, 2012

Abstract (private)

ICAMM2012-extended-abstract-vandichel.pdf

Conference reference

VASP & ICAMM 2012

Selectivity prediction for the citronellal cyclization on Cu3BTC2: a comparison between extended cluster and periodic calculations

wim — Mon, 02 Jul 2012 14:00:04 +0000

M. Vandichel, F. Vermoortele, S. Cottenie, D. De Vos, M. Waroquier, V. Van Speybroeck

p. 93-94

Poster

Conference / event / venue

ICTAC-14

Vlissingen, The Netherlands

Tuesday, 26 June, 2012 to Saturday, 30 June, 2012

Abstract (private)

2012_ICTAC14_MVandichel.pdf

Conference reference

ICTAC-14

Selectivity prediction for the citronellal cyclization on various catalysts

wim — Tue, 20 Mar 2012 08:20:43 +0000

M. Vandichel, S. Cottenie, F. Vermoortele, D. De Vos, M. Waroquier, V. Van Speybroeck

Poster

Conference / event / venue

IAP Annual Meeting

Leuven, Belgium

Monday, 21 November, 2011 to Tuesday, 22 November, 2011

Abstract (private)

IAP_2011_Vandichel_Cottenie_citronellal_cyclization.pdf

Conference reference

Annual Meeting for Interuniversity Attraction Poles (IUAP) 2011

Modeling citronellal cyclization in Cu3BTC2 and UiO-66

wim — Mon, 17 Oct 2011 13:22:38 +0000

M. Vandichel, S. Cottenie, F. Vermoortele, D. De Vos, M. Waroquier, V. Van Speybroeck

Poster

Conference / event / venue

IAP FS2 6/27 Annual Network Meeting

Brussels, Belgium

Monday, 29 November, 2010 to Tuesday, 30 November, 2010

Abstract

IAP FS2 6_abstract_Vandichel.pdf

Modelling citronellal cyclization in Cu3(BTC)2

wim — Mon, 17 Oct 2011 13:14:47 +0000

S. Cottenie, M. Vandichel, F. Vermoortele, D. De Vos, M. Waroquier, V. Van Speybroeck

p. 349

Poster

Conference / event / venue

XIIth Netherlands' Catalysis and Chemistry Conference (NCCC XII)

Noordwijkerhout, The Netherlands

Monday, 28 February, 2011 to Wednesday, 2 March, 2011

Abstract

2011 nccc SCottenie.pdf

Conference reference

NCCC-XII

Modeling Lewis catalyzed reactions in Metal Organic Frameworks

wim — Fri, 26 Aug 2011 13:20:52 +0000

M. Vandichel, S. Cottenie, F. Vermoortele, D. De Vos, M. Waroquier, V. Van Speybroeck

p. 120

Talk

Conference / event / venue

XIIth Netherlands' Catalysis and Chemistry Conference

Noordwijkerhout, The Netherlands

Monday, 28 February, 2011 to Wednesday, 2 March, 2011

Abstract

2011M_Vandichel_ncccc.pdf

Conference reference

NCCC-XII

Stijn Cottenie

wim — Thu, 25 Aug 2011 12:19:38 +0000