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Mechanistic Studies on the Nucleophilic Reaction of Porphyrins with Organolithium Reagents

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Institut für Chemie, Organische Chemie, Freie Universität Berlin, Takustr. 3, D-14195 Berlin, Germany
Cite this: J. Org. Chem. 2001, 66, 26, 8693–8700
Publication Date (Web):October 4, 2001
https://doi.org/10.1021/jo010559x
Copyright © 2001 American Chemical Society
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    Abstract

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    Porphyrins react readily with organolithium reagents under substitution of free meso positions. As this method has proven to be very versatile for the preparation of a wide range of meso substituted porphyrins, a mechanistic study of the reaction was undertaken using 5,15-diaryl- and dialkyl substituted porphyrins, 2,3,7,8,12,13,17,18-octaethylporphyrin, and the respective nickel(II) complexes. A combination of deuteration experiments, electronic absorption spectroscopy of the reactive intermediates, trapping of intermediates with organic electrophiles, and reaction at different pH values showed significant differences in the reaction pathways of free base porphyrins and metalloporphyrins. In both cases the reaction proceeds initially under formation of phlorin like intermediates which are stable in water. For the Ni(II)phlorins a mesomeric carbanionic form with a highly distorted structure exists that can react as a nucleophile with electrophiles such as RI, H+, or D+. In the latter case a protonation-deprotonation equilibrium involving porphodimethen intermediates has to be assumed. Free base phlorins do not react as nucleophiles but can undergo H/D exchange reactions in strongly acidic media.

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    1H NMR spectra of 9, 10, 11, 14, 15, 18, 19, 20, and 22. This material is available free of charge via the Internet at http://pubs.acs.org.

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    36. Mathias O. Senge, Julia Richter. Synthetic transformations of porphyrins – Advances 2002-2004. Journal of Porphyrins and Phthalocyanines 2004, 08 (07) , 934-953. https://doi.org/10.1142/S1088424604000313
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    38. Regan D. Hartnell, Dennis P. Arnold. Peripherally Metallated Porphyrins: the First Examples of meso ‐η 1 ‐Palladio( II ) and ‐Platinio( II ) Complexes with Chelating Diamine Ligands. European Journal of Inorganic Chemistry 2004, 2004 (6) , 1262-1269. https://doi.org/10.1002/ejic.200300600
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    41. Neeraj Agarwal, C.‐H. Hung, M. Ravikanth. Thiaporphyrins with One, Two and Four Unsubstituted meso ‐Carbons: Synthesis and Functionalization. European Journal of Organic Chemistry 2003, 2003 (19) , 3730-3734. https://doi.org/10.1002/ejoc.200300333
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