Modulation of the reactivity, stability and substrate- and enantioselectivity of an epoxidation catalyst by noncovalent dynamic attachment of a receptor functionality - aspects on the mechanism of the Jacobsen-Katsuki epoxidation applied to a supramolecular system
(2006) In Organic and Biomolecular Chemistry 4(10). p.1927-1948- Abstract
- The synthesis of the components of the dynamic supramolecular hydrogen-bonded catalytic system 2 + 3 is described. The catalytic performance and substrate- and enantioselectivity of Mn(salen) catalyst 2 were investigated in the presence and absence of the Zn(porphyrin) receptor unit 3. The effects of pyridine and pyridine N-oxide donor ligands were also studied. Some aspects on the mechanism of the Jacobsen - Katsuki epoxidation, based on literature observations, are introduced as a means to analyse the behaviour of 2 and its modulation by the formation of macrocycle 1 with 3. A complete association model of the metal-free system 4 + 5 refutes the earlier assumption that macrocycle 1 is the predominant form of catalyst 2 under the standard... (More)
- The synthesis of the components of the dynamic supramolecular hydrogen-bonded catalytic system 2 + 3 is described. The catalytic performance and substrate- and enantioselectivity of Mn(salen) catalyst 2 were investigated in the presence and absence of the Zn(porphyrin) receptor unit 3. The effects of pyridine and pyridine N-oxide donor ligands were also studied. Some aspects on the mechanism of the Jacobsen - Katsuki epoxidation, based on literature observations, are introduced as a means to analyse the behaviour of 2 and its modulation by the formation of macrocycle 1 with 3. A complete association model of the metal-free system 4 + 5 refutes the earlier assumption that macrocycle 1 is the predominant form of catalyst 2 under the standard epoxidation reaction conditions with 2 + 3. Evidence are provided that receptor-binding substrates and nonbinding substrates, respectively, are epoxidised by two different catalytic species, or two distinct distributions of species in competitive epoxidations using catalytic system 2 + 3. The two species are assigned to the endo and exo faces of the Mn( salen) catalyst in macrocycle 1, and to equivalently folded oligomeric structures with monomers 2 and 3 in adjacent positions. (Less)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/409982
- author
- Jonsson, Stefan LU ; Odille, Fabrice LU ; Norrby, Per-Ola and Wärnmark, Kenneth LU
- organization
- publishing date
- 2006
- type
- Contribution to journal
- publication status
- published
- subject
- in
- Organic and Biomolecular Chemistry
- volume
- 4
- issue
- 10
- pages
- 1927 - 1948
- publisher
- Royal Society of Chemistry
- external identifiers
-
- wos:000237462400014
- scopus:33646743586
- pmid:16688339
- ISSN
- 1477-0539
- DOI
- 10.1039/b518244a
- language
- English
- LU publication?
- yes
- additional info
- The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Organic chemistry (S/LTH) (011001240)
- id
- f7229d83-c9c2-4fa8-9a0c-e0e0c75449d5 (old id 409982)
- date added to LUP
- 2016-04-01 11:46:31
- date last changed
- 2022-04-20 21:36:09
@article{f7229d83-c9c2-4fa8-9a0c-e0e0c75449d5,
abstract = {{The synthesis of the components of the dynamic supramolecular hydrogen-bonded catalytic system 2 + 3 is described. The catalytic performance and substrate- and enantioselectivity of Mn(salen) catalyst 2 were investigated in the presence and absence of the Zn(porphyrin) receptor unit 3. The effects of pyridine and pyridine N-oxide donor ligands were also studied. Some aspects on the mechanism of the Jacobsen - Katsuki epoxidation, based on literature observations, are introduced as a means to analyse the behaviour of 2 and its modulation by the formation of macrocycle 1 with 3. A complete association model of the metal-free system 4 + 5 refutes the earlier assumption that macrocycle 1 is the predominant form of catalyst 2 under the standard epoxidation reaction conditions with 2 + 3. Evidence are provided that receptor-binding substrates and nonbinding substrates, respectively, are epoxidised by two different catalytic species, or two distinct distributions of species in competitive epoxidations using catalytic system 2 + 3. The two species are assigned to the endo and exo faces of the Mn( salen) catalyst in macrocycle 1, and to equivalently folded oligomeric structures with monomers 2 and 3 in adjacent positions.}},
author = {{Jonsson, Stefan and Odille, Fabrice and Norrby, Per-Ola and Wärnmark, Kenneth}},
issn = {{1477-0539}},
language = {{eng}},
number = {{10}},
pages = {{1927--1948}},
publisher = {{Royal Society of Chemistry}},
series = {{Organic and Biomolecular Chemistry}},
title = {{Modulation of the reactivity, stability and substrate- and enantioselectivity of an epoxidation catalyst by noncovalent dynamic attachment of a receptor functionality - aspects on the mechanism of the Jacobsen-Katsuki epoxidation applied to a supramolecular system}},
url = {{http://dx.doi.org/10.1039/b518244a}},
doi = {{10.1039/b518244a}},
volume = {{4}},
year = {{2006}},
}