Fe(PyTACN)-catalyzed cis-dihydroxylation of olefins with hydrogen peroxide
dc.contributor.author
dc.date.accessioned
2016-03-15T11:35:44Z
dc.date.available
2016-03-15T11:35:44Z
dc.date.issued
2013
dc.identifier.issn
1615-4150
dc.identifier.uri
dc.description.abstract
A family of iron complexes with general formula [Fe(II)( R,Y,XPyTACN)(CF3SO3)2], where R,Y,XPyTACN=1-[2′-(4-Y-6-X-pyridyl)methyl]-4,7-dialkyl-1,4, 7-triazacyclononane, X and Y refer to the groups at positions 4 and 6 of the pyridine, respectively, and R refers to the alkyl substitution at N-4 and N-7 of the triazacyclononane ring, are shown to be catalysts for efficient and selective alkene oxidation (epoxidation and cis-dihydroxylation) employing hydrogen peroxide as oxidant. Complex [Fe(II)(Me,Me,HPyTACN)(CF 3SO3)2] (7), was identified as the most efficient and selective cis-dihydroxylation catalyst among the family. The high activity of 7 allows the oxidation of alkenes to proceed rapidly (30 min) at room temperature and under conditions where the olefin is not used in large amounts but instead is the limiting reagent. In the presence of 3 mol% of 7, 2 equiv. of H2O2 as oxidant and 15 equiv. of water, in acetonitrile solution, alkenes are cis-dihydroxylated reaching yields that might be interesting for synthetic purposes. Competition experiments show that 7 exhibits preferential selectivity towards the oxidation of cis olefins over the trans analogues, and also affords better yields and high [syn-diol]/[epoxide] ratios when cis olefins are oxidized. For aliphatic substrates, reaction yields attained with the present system compare favourably with state of the art Fe-catalyzed cis-dihydroxylation systems, and it can be regarded as an attractive complement to the iron and manganese systems described recently and which show optimum activity against electron-deficient and aromatic olefins
dc.description.sponsorship
Financial support by ERC-29910, MCYT of Spain through project CTQ2009-08464/BQU to MC. IP, and MC thank MICINN and Generalitat de Catalunya, respectively for PhD grants. MC and XR thank Generalitat de Catalunya for 2009SGR637 and ICREA Acad mia Awards. XR is grateful for finanical support from INNPLANTA project IPN-2011-0059-PCT-42000-ACT1
dc.format.mimetype
application/pdf
dc.language.iso
eng
dc.publisher
Wiley-VCH Verlag
dc.relation
MICINN/PN 2011/INP-2011-0059-PCT-420000
MICINN/PN 2010-2012/ CTQ2009-08464
AGAUR/2009-2014/2009 SGR-637
dc.relation.isformatof
Reproducció digital del document publicat a: http://dx.doi.org/10.1002/adsc.201200938
dc.relation.ispartof
© Advanced Synthesis and Catalysis, 2013, vol. 355, núm. 5, p. 947-956
dc.relation.ispartofseries
Articles publicats (D-Q)
dc.rights
Tots els drets reservats
dc.subject
dc.title
Fe(PyTACN)-catalyzed cis-dihydroxylation of olefins with hydrogen peroxide
dc.type
info:eu-repo/semantics/article
dc.rights.accessRights
info:eu-repo/semantics/embargoedAccess
dc.embargo.terms
Cap
dc.date.embargoEndDate
info:eu-repo/date/embargoEnd/2026-01-01
dc.type.version
info:eu-repo/semantics/publishedVersion
dc.identifier.doi
dc.identifier.idgrec
017183
dc.contributor.funder
dc.identifier.eissn
1615-4169