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S. C. Virgil et al.
SHORT COMMUNICATION
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in the Supporting Information and increase with the number
of chromophoric aryl residues present in each oligomer.
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of equal proportions of d, l, meso1 and meso2 isomers that
1
would afford a 1:1:2 ratio of peaks in the H NMR spectrum.
[15] Our finding is in accordance with the report by Lee (ref.[16b]
)
and a report by Gryko (ref.[16c]) in which the isolation of analo-
gous corrole precursors similar to 6 was reported.
[16] a) D. T. Gryko, K. Jadach, J. Org. Chem. 2001, 66, 4267–4275;
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[4]
[17] The key cyclization of an electron-deficient intermediate during
the DDQ oxidation of 6 could also involve a radical intermedi-
ate analogous to that shown in Scheme 4. The progress of the
DDQ oxidation of 6 is shown in the Supporting Information
and may exhibit features particular to this electron-deficient
perfluoroaryl series.
[18] Of the two possible tautomeric representations of 1, the struc-
ture presented in Figure 3 unambiguously reveals the position
of the three central hydrogen atoms. As shown in Scheme 1,
two hydrogen atoms are found on the intact bipyrrole subunit
and one hydrogen atom is shared within the top tautomeric
portion of corrole 1. See the Supporting Information for more
details. CCDC-1052621 contains the supplementary crystallo-
graphic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
[5]
[6]
[7]
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203, 107–114.
[9] G. R. Geier III, J. S. Lindsey, J. Chem. Soc. Perkin Trans. 2
2001, 677–686.
[10] The specific conditions for the condensation of equimolar
amounts of 2 and 3 affording cyclic and Ar-terminal products
have been previously reported, see: L. Simkhovich, I. Gold-
berg, Z. Gross, Org. Lett. 2003, 5, 1241–1244.
[11] Although reaction of 2 and 3 can be treated as a classical step-
growth oligomerization to generate a weight distribution of
oligomers 4–10 favoring compound 6, the strong predominance
of 6 obtained in this procedure arises from the attenuated reac-
tivities of the sequential intermediates 4–10 and the lower rela-
tive reactivity of pyrrole, see: P. J. Flory, Principles of Polymer
Chemistry, Cornell University Press, New York, 1953, ch. 8.
[12] On the 20 g scale presented in this work, the condensation reac-
tion was evaluated under both air and nitrogen atmosphere
and the product distribution shown in Figure 1was found to be
identical under both conditions. Molar response factors mea-
sured at 254 nm for the purified oligomers 4–10 are provided
[19] In addition to the procedures presented in ref.[1,2], one can
compare this work with previously reported procedures for the
preparation of 1, see: a) I. H. Wasbotten, T. Wondimagegn, A.
Ghosh, J. Am. Chem. Soc. 2002, 124, 8104–8116; b) D. T.
Gryko, B. Koszarna, Org. Biomol. Chem. 2003, 1, 350–357; c)
D. K. Dogutan, S. A. Stoian, R. McGuire Jr., M. Schwalbe,
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140.
Received: February 27, 2015
Published Online:
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