---
_id: '64019'
abstract:
- lang: eng
  text: A chiral zirconium-based catalyst, DUT-67-Pro containing 8-connected Zr6-clusters
    is obtained by post synthetic functionalization of Zr6O6(OH)2(TDC)4(HCOO)2 (DUT-67,
    TDC = 2,5-thiophenedicarboxylate) with the chiral monocarboxylic acid, L-proline.
    13C and 15N solid state MAS and DNP NMR studies of DUT-67-Pro confirm the integration
    of L-proline into the porous framework. The chiral MOF catalyst exhibits an excellent
    catalytic activity at low temperature (298 K) with an unprecedented syn-(S,S)-product
    selectivity in an asymmetric aldol addition reaction of cyclohexanone to 4-nitrobenzaldehyde
    (yield = 95%, ee = 96%). Comparative catalytic studies using a molecular Zr6-cluster
    model compound indicate the Zr6-moiety to be responsible for this inverse diastereoselectivity
    compared to well-established L-proline organocatalysis and a mechanism is proposed
    to explain the Zr6-cluster-mediated syn-selectivity. Masking residual acidic active
    sites in the cluster of the framework was found to be a key prerequisite to achieve
    the high enantioselectivity. The purely heterogeneous catalytic system based on
    DUT-67-Pro is highly stable and can be recycled several times.
author:
- first_name: Khoa D.
  full_name: Nguyen, Khoa D.
  last_name: Nguyen
- first_name: Christel
  full_name: Kutzscher, Christel
  last_name: Kutzscher
- first_name: Sebastian
  full_name: Ehrling, Sebastian
  last_name: Ehrling
- first_name: Irena
  full_name: Senkovska, Irena
  last_name: Senkovska
- first_name: Volodymyr
  full_name: Bon, Volodymyr
  last_name: Bon
- first_name: Marcos
  full_name: Oliveira, Marcos
  last_name: Oliveira
- first_name: Torsten
  full_name: Gutmann, Torsten
  id: '118165'
  last_name: Gutmann
- first_name: Gerd
  full_name: Buntkowsky, Gerd
  last_name: Buntkowsky
- first_name: Stefan
  full_name: Kaskel, Stefan
  last_name: Kaskel
citation:
  ama: Nguyen KD, Kutzscher C, Ehrling S, et al. Insights into the role of zirconium
    in proline functionalized metal-organic frameworks attaining high enantio- and
    diastereoselectivity. <i>Journal of Catalysis</i>. 2019;377:41–50. doi:<a href="https://doi.org/10.1016/j.jcat.2019.07.003">10.1016/j.jcat.2019.07.003</a>
  apa: Nguyen, K. D., Kutzscher, C., Ehrling, S., Senkovska, I., Bon, V., Oliveira,
    M., Gutmann, T., Buntkowsky, G., &#38; Kaskel, S. (2019). Insights into the role
    of zirconium in proline functionalized metal-organic frameworks attaining high
    enantio- and diastereoselectivity. <i>Journal of Catalysis</i>, <i>377</i>, 41–50.
    <a href="https://doi.org/10.1016/j.jcat.2019.07.003">https://doi.org/10.1016/j.jcat.2019.07.003</a>
  bibtex: '@article{Nguyen_Kutzscher_Ehrling_Senkovska_Bon_Oliveira_Gutmann_Buntkowsky_Kaskel_2019,
    title={Insights into the role of zirconium in proline functionalized metal-organic
    frameworks attaining high enantio- and diastereoselectivity}, volume={377}, DOI={<a
    href="https://doi.org/10.1016/j.jcat.2019.07.003">10.1016/j.jcat.2019.07.003</a>},
    journal={Journal of Catalysis}, author={Nguyen, Khoa D. and Kutzscher, Christel
    and Ehrling, Sebastian and Senkovska, Irena and Bon, Volodymyr and Oliveira, Marcos
    and Gutmann, Torsten and Buntkowsky, Gerd and Kaskel, Stefan}, year={2019}, pages={41–50}
    }'
  chicago: 'Nguyen, Khoa D., Christel Kutzscher, Sebastian Ehrling, Irena Senkovska,
    Volodymyr Bon, Marcos Oliveira, Torsten Gutmann, Gerd Buntkowsky, and Stefan Kaskel.
    “Insights into the Role of Zirconium in Proline Functionalized Metal-Organic Frameworks
    Attaining High Enantio- and Diastereoselectivity.” <i>Journal of Catalysis</i>
    377 (2019): 41–50. <a href="https://doi.org/10.1016/j.jcat.2019.07.003">https://doi.org/10.1016/j.jcat.2019.07.003</a>.'
  ieee: 'K. D. Nguyen <i>et al.</i>, “Insights into the role of zirconium in proline
    functionalized metal-organic frameworks attaining high enantio- and diastereoselectivity,”
    <i>Journal of Catalysis</i>, vol. 377, pp. 41–50, 2019, doi: <a href="https://doi.org/10.1016/j.jcat.2019.07.003">10.1016/j.jcat.2019.07.003</a>.'
  mla: Nguyen, Khoa D., et al. “Insights into the Role of Zirconium in Proline Functionalized
    Metal-Organic Frameworks Attaining High Enantio- and Diastereoselectivity.” <i>Journal
    of Catalysis</i>, vol. 377, 2019, pp. 41–50, doi:<a href="https://doi.org/10.1016/j.jcat.2019.07.003">10.1016/j.jcat.2019.07.003</a>.
  short: K.D. Nguyen, C. Kutzscher, S. Ehrling, I. Senkovska, V. Bon, M. Oliveira,
    T. Gutmann, G. Buntkowsky, S. Kaskel, Journal of Catalysis 377 (2019) 41–50.
date_created: 2026-02-07T16:02:33Z
date_updated: 2026-02-17T16:14:42Z
doi: 10.1016/j.jcat.2019.07.003
extern: '1'
intvolume: '       377'
keyword:
- -proline
- -selective aldol reaction
- Chirality
- Metal-organic framework
- Zirconium
language:
- iso: eng
page: 41–50
publication: Journal of Catalysis
status: public
title: Insights into the role of zirconium in proline functionalized metal-organic
  frameworks attaining high enantio- and diastereoselectivity
type: journal_article
user_id: '100715'
volume: 377
year: '2019'
...