PMID: 11902894Mar 21, 2002Paper

Olefin cis-dihydroxylation versus epoxidation by non-heme iron catalysts: two faces of an Fe(III)-OOH coin

Journal of the American Chemical Society
Kui ChenLawrence Que

Abstract

The oxygenation of carbon-carbon double bonds by iron enzymes generally results in the formation of epoxides, except in the case of the Rieske dioxygenases, where cis-diols are produced. Herein we report a systematic study of olefin oxidations with H(2)O(2) catalyzed by a group of non-heme iron complexes, i.e., [Fe(II)(BPMEN)(CH(3)CN)(2)](2+) (1, BPMEN = N,N'-dimethyl-N,N'-bis(2-pyridylmethyl)-1,2-diaminoethane) and [Fe(II)(TPA)(CH(3)CN)(2)](2+) (4, TPA = tris(2-pyridylmethyl)amine) and their 6- and 5-methyl-substituted derivatives. We demonstrate that olefin epoxidation and cis-dihydroxylation are different facets of the reactivity of a common Fe(III)-OOH intermediate, whose spin state can be modulated by the electronic and steric properties of the ligand environment. Highly stereoselective epoxidation is favored by catalysts with no more than one 6-methyl substituent, which give rise to low-spin Fe(III)-OOH species (category A). On the other hand, cis-dihydroxylation is favored by catalysts with more than one 6-methyl substituent, which afford high-spin Fe(III)-OOH species (category B). For catalysts in category A, both the epoxide and the cis-diol product incorporate (18)O from H(2)(18)O, results that implicate a cis-H(18)O-...Continue Reading

References

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Citations

Jul 28, 2006·Chemistry : a European Journal·Rubén Mas-BallestéLawrence Que
Aug 28, 2007·Chemistry : a European Journal·Geoffroy GuillemotAndreas Pfaltz
Nov 21, 2007·Chemistry : a European Journal·Pieter C A BruijnincxRobertus J M Klein Gebbink
May 9, 2008·Chemical Communications : Chem Comm·Xiaopeng Shan, Lawrence Que
Aug 30, 2008·Dalton Transactions : an International Journal of Inorganic Chemistry·Lok H TongJonathan R Dilworth
Aug 8, 2008·Chemical Communications : Chem Comm·Ho-Lun YeungHoi-Lun Kwong
Nov 6, 2008·Dalton Transactions : an International Journal of Inorganic Chemistry·Johannes W de BoerBen L Feringa
Feb 25, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Mohammad S Askari, Xavier Ottenwaelder
Jun 3, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·Xavier Solans-MonfortRubén Mas-Ballesté
Dec 3, 2013·Chemical Communications : Chem Comm·Olga V MakhlynetsElena V Rybak-Akimova
Jan 23, 2014·Organic & Biomolecular Chemistry·Vital A YazerskiRobertus J M Klein Gebbink
Oct 14, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Michaela GrauGeorge J P Britovsek
Sep 25, 2014·Chemical Communications : Chem Comm·Shyam R IyerLawrence Que
Feb 11, 2016·Biotechnology for Biofuels·Aditya BhallaEric L Hegg
Jan 12, 2017·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Subhasree Kal, Lawrence Que
Jan 27, 2017·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Giorgio OlivoMiquel Costas
Jul 22, 2018·Chemical Communications : Chem Comm·Shuangning XuLawrence Que
Feb 24, 2019·Nature Communications·Margarida BorrellMiquel Costas
Sep 19, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Denan WangSergey V Lindeman
Jan 18, 2020·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Angela PariseTiziana Marino
Feb 15, 2007·Chemical Communications : Chem Comm·Gopinathan AnilkumarMatthias Beller
Jun 30, 2009·Dalton Transactions : an International Journal of Inorganic Chemistry·Ramasamy MayilmuruganMallayan Palaniandavar
Jul 1, 2009·Dalton Transactions : an International Journal of Inorganic Chemistry·Jason EnglandGeorge J P Britovsek
Aug 24, 2007·Chemical Communications : Chem Comm·Katie L KlotzJason A Halfen
Oct 31, 2009·Chemistry : a European Journal·Olga V MakhlynetsLawrence Que
Oct 26, 2005·Chemical Communications : Chem Comm·Sonia TaktakElena V Rybak-Akimova
Sep 19, 2008·Nature·Lawrence Que, William B Tolman
Oct 28, 2009·Dalton Transactions : an International Journal of Inorganic Chemistry·Aurore ThibonFrédéric Banse
Dec 1, 2010·Chemistry : a European Journal·Olga V Makhlynets, Elena V Rybak-Akimova
Aug 18, 2010·Organic & Biomolecular Chemistry·Pattama SaisahaWesley R Browne
Nov 5, 2010·Chemical Society Reviews·Carole J R Bataille, Timothy J Donohoe
Sep 24, 2011·Nature Chemistry·Aidan R McDonald, Lawrence Que
Jun 20, 2012·Chemical Science·Ji-Bao XiaChuo Chen
Mar 5, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·Cristina M CoatesChristian R Goldsmith
Aug 7, 2010·Bioinorganic Chemistry and Applications·Giorgos Bilis, Maria Louloudi
Jul 24, 2012·Angewandte Chemie·Shota KoyaTsutomu Katsuki

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