Manganese catalysts with molecular recognition functionality for selective alkene epoxidation

F. Jonathan, Hull Effiette L O Sauer, Christopher D. Incarvito, J. W. Faller, Gary W Brudvig, Robert H. Crabtree

Research output: Contribution to journalArticle

27 Citations (Scopus)

Abstract

Selective epoxidation of alkenes is possible with a new manganese porphyrin catalyst, C PMR, that uses hydrogen bonding between the carboxylic acid on the substrate molecule and a Kemp's triacid unit. For two out of three olefin substrates employed, molecular recognition prevents the unselective oxidation of C-H bonds, and directs oxidation to the olefin moiety, giving only epoxide products. Weak diastereoselectivity is observed in the epoxide products, suggesting that molecular recognition affects the orientation of the catalyst-bound substrate. The previously reported manganese terpyridine complex C TMR is shown to be a superior epoxidation catalyst to the porphyrin catalyst C PMR. Good conversion of 2-cyclopentene acetic acid (substrate S2) with C PMR is consistent with molecular modeling, which indicates a particularly good substrate/catalyst match. Evidence suggests that hydrogen bonding between the substrate and the catalyst is critical in this system.

Original languageEnglish
Pages (from-to)488-495
Number of pages8
JournalInorganic Chemistry
Volume48
Issue number2
DOIs
Publication statusPublished - Jan 19 2009

Fingerprint

Molecular recognition
epoxidation
Epoxidation
Alkenes
Manganese
alkenes
manganese
catalysts
Catalysts
Substrates
epoxy compounds
Epoxy Compounds
Porphyrins
porphyrins
Hydrogen bonds
Cyclopentanes
Oxidation
oxidation
Molecular modeling
hydrogen

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Jonathan, F., Sauer, H. E. L. O., Incarvito, C. D., Faller, J. W., Brudvig, G. W., & Crabtree, R. H. (2009). Manganese catalysts with molecular recognition functionality for selective alkene epoxidation. Inorganic Chemistry, 48(2), 488-495. https://doi.org/10.1021/ic8013464

Manganese catalysts with molecular recognition functionality for selective alkene epoxidation. / Jonathan, F.; Sauer, Hull Effiette L O; Incarvito, Christopher D.; Faller, J. W.; Brudvig, Gary W; Crabtree, Robert H.

In: Inorganic Chemistry, Vol. 48, No. 2, 19.01.2009, p. 488-495.

Research output: Contribution to journalArticle

Jonathan, F, Sauer, HELO, Incarvito, CD, Faller, JW, Brudvig, GW & Crabtree, RH 2009, 'Manganese catalysts with molecular recognition functionality for selective alkene epoxidation', Inorganic Chemistry, vol. 48, no. 2, pp. 488-495. https://doi.org/10.1021/ic8013464
Jonathan, F. ; Sauer, Hull Effiette L O ; Incarvito, Christopher D. ; Faller, J. W. ; Brudvig, Gary W ; Crabtree, Robert H. / Manganese catalysts with molecular recognition functionality for selective alkene epoxidation. In: Inorganic Chemistry. 2009 ; Vol. 48, No. 2. pp. 488-495.
@article{9d9fa8edc571417f90f43e8100368b7c,
title = "Manganese catalysts with molecular recognition functionality for selective alkene epoxidation",
abstract = "Selective epoxidation of alkenes is possible with a new manganese porphyrin catalyst, C PMR, that uses hydrogen bonding between the carboxylic acid on the substrate molecule and a Kemp's triacid unit. For two out of three olefin substrates employed, molecular recognition prevents the unselective oxidation of C-H bonds, and directs oxidation to the olefin moiety, giving only epoxide products. Weak diastereoselectivity is observed in the epoxide products, suggesting that molecular recognition affects the orientation of the catalyst-bound substrate. The previously reported manganese terpyridine complex C TMR is shown to be a superior epoxidation catalyst to the porphyrin catalyst C PMR. Good conversion of 2-cyclopentene acetic acid (substrate S2) with C PMR is consistent with molecular modeling, which indicates a particularly good substrate/catalyst match. Evidence suggests that hydrogen bonding between the substrate and the catalyst is critical in this system.",
author = "F. Jonathan and Sauer, {Hull Effiette L O} and Incarvito, {Christopher D.} and Faller, {J. W.} and Brudvig, {Gary W} and Crabtree, {Robert H.}",
year = "2009",
month = "1",
day = "19",
doi = "10.1021/ic8013464",
language = "English",
volume = "48",
pages = "488--495",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "2",

}

TY - JOUR

T1 - Manganese catalysts with molecular recognition functionality for selective alkene epoxidation

AU - Jonathan, F.

AU - Sauer, Hull Effiette L O

AU - Incarvito, Christopher D.

AU - Faller, J. W.

AU - Brudvig, Gary W

AU - Crabtree, Robert H.

PY - 2009/1/19

Y1 - 2009/1/19

N2 - Selective epoxidation of alkenes is possible with a new manganese porphyrin catalyst, C PMR, that uses hydrogen bonding between the carboxylic acid on the substrate molecule and a Kemp's triacid unit. For two out of three olefin substrates employed, molecular recognition prevents the unselective oxidation of C-H bonds, and directs oxidation to the olefin moiety, giving only epoxide products. Weak diastereoselectivity is observed in the epoxide products, suggesting that molecular recognition affects the orientation of the catalyst-bound substrate. The previously reported manganese terpyridine complex C TMR is shown to be a superior epoxidation catalyst to the porphyrin catalyst C PMR. Good conversion of 2-cyclopentene acetic acid (substrate S2) with C PMR is consistent with molecular modeling, which indicates a particularly good substrate/catalyst match. Evidence suggests that hydrogen bonding between the substrate and the catalyst is critical in this system.

AB - Selective epoxidation of alkenes is possible with a new manganese porphyrin catalyst, C PMR, that uses hydrogen bonding between the carboxylic acid on the substrate molecule and a Kemp's triacid unit. For two out of three olefin substrates employed, molecular recognition prevents the unselective oxidation of C-H bonds, and directs oxidation to the olefin moiety, giving only epoxide products. Weak diastereoselectivity is observed in the epoxide products, suggesting that molecular recognition affects the orientation of the catalyst-bound substrate. The previously reported manganese terpyridine complex C TMR is shown to be a superior epoxidation catalyst to the porphyrin catalyst C PMR. Good conversion of 2-cyclopentene acetic acid (substrate S2) with C PMR is consistent with molecular modeling, which indicates a particularly good substrate/catalyst match. Evidence suggests that hydrogen bonding between the substrate and the catalyst is critical in this system.

UR - http://www.scopus.com/inward/record.url?scp=60849133905&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=60849133905&partnerID=8YFLogxK

U2 - 10.1021/ic8013464

DO - 10.1021/ic8013464

M3 - Article

VL - 48

SP - 488

EP - 495

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 2

ER -