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Preparation of Furan and Thiophene-Derived Fulvene Dialdehydes: Synthesis and Structural Characterization of a 22-Oxa-21-carbaporphyrin and a Related Palladium(II) Organometallic Complex†

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Department of Chemistry, Illinois State University, Normal, Illinois 61790-4160
[email protected]
Cite this: J. Org. Chem. 2010, 75, 19, 6563–6573
Publication Date (Web):September 9, 2010
https://doi.org/10.1021/jo101310m
Copyright © 2010 American Chemical Society
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    Abstract

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    A series of fulvene monoaldehydes were prepared by reacting furan or thiophene carbaldehydes with an indene-derived enamine in the presence of di-n-butylboron triflate, but considerable difficulties were encountered in the preparation of fulvene dialdehydes needed for the synthesis of novel porphyrin analogues. These problems were overcome by reacting protected iodofulvenes with magnesium ate complexes at low temperatures, followed by addition of DMF and hydrolysis. The thiophene-containing fulvene gave good yields of the dialdehyde at −78 °C or −100 °C, but the furan system gave a major byproduct formally derived from valeraldehyde under the higher temperature conditions. This compound was fully characterized by NMR spectroscopy, mass spectrometry, and X-ray crystallography. However, this side reaction could be completely avoided at −100 °C, and the required furan-containing fulvene dialdehyde was isolated in 46% yield. The furan-derived dialdehyde reacted with a dipyrrylmethane in the presence of trifluoroacetic acid to give the 22-oxa-21-carbaporphyrin 19 in excellent yields (73−79%). However, the thiophene-containing fulvene dialdehyde failed to give any of the anticipated macrocyclic product. An unstable acyclic intermediate was isolated and partially characterized, but this species could not be induced to cyclize. Steric factors may play a role, but X-ray crystallography confirmed that the fulvene dialdehyde precursor does have the correct geometry to facilitate the formation of the porphyrinoid macrocycle. The new oxacarbaporphyrin was fully characterized and could easily be converted into the corresponding mono- and dicationic species. The second protonation involves addition onto the internal indene carbon and proton NMR spectroscopy for the sample in HCl−TFA demonstrates that it retains strongly diatropic characteristics. The free base oxacarbaporphyrin reacted with Pd(OAc)2 in DMF to give the corresponding palladium(II) organometallic derivative 27. The proton NMR spectrum for this complex also shows the retention of a strong, albeit slightly reduced, diatropic ring current. The free base oxacarbaporphyrin and the palladium derivative were both structurally characterized by X-ray crystallography. The bond lengths for 19 and 27 were consistent with the presence of significant 18π-electron delocalization pathways.

    Part 55 in the series “Conjugated Macrocycles Related to the Porphyrins”. For part 54, see: Lash, T. D.; Jones, S. A.; Ferrence, G. M. J. Am. Chem. Soc.2010, published ASAP August 25, 2010; DOI: 10.1021/ja105146a.

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    Crystallographic data for 19, 22f, 26, and 27 in CIF format and experimental details for the X-ray structure determinations are provided, together with ORTEP-III figures, MS, UV−vis, 1H NMR, and 13C NMR spectra for selected compounds. This material is available free of charge via the Internet at http://pubs.acs.org.

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    Cited By

    This article is cited by 27 publications.

    1. Fan Luo, Runa A, Xiangshen Sun, Yuefa Gong. Regioselective Synthesis of 6-Chlorofulvene and 6-Aminofulvene via Keto–Enol Tautomerism. Journal of Chemical Education 2020, 97 (10) , 3829-3834. https://doi.org/10.1021/acs.jchemed.0c00039
    2. Jeyun Jo, Myeonggyo Jeong, Ji-Su Ahn, Jinia Akter, Hyung-Sik Kim, Young-Ger Suh, Hwayoung Yun. Total Synthesis of Anmindenol A and Its Application to the Design, Synthesis, and Biological Evaluation of Derivatives Thereof. The Journal of Organic Chemistry 2019, 84 (17) , 10953-10961. https://doi.org/10.1021/acs.joc.9b01564
    3. Pankaj Jain, Deyaa I. AbuSalim, Timothy D. Lash. adj-Dicarbaporphyrinoid Systems: Synthesis, Spectroscopic Characterization, and Reactivity of 23-Carbabenziporphyrins. The Journal of Organic Chemistry 2019, 84 (16) , 10237-10256. https://doi.org/10.1021/acs.joc.9b01410
    4. Timothy D. Lash, Stacy C. Fosu, Tyler J. Smolczyk, Deyaa I. AbuSalim. Synthesis of Expanded Porphyrinoids with Azulene and Indene Subunits and an opp-Dioxadicarbaporphyrin from Fulvene Carbinols and a Dioxacarbatripyrrin. The Journal of Organic Chemistry 2018, 83 (20) , 12619-12631. https://doi.org/10.1021/acs.joc.8b01929
    5. Timothy D. Lash and Gregory M. Ferrence . Metalation and Selective Oxidation of Diphenyl-23-oxa-, -thia-, and -selena-21-carbaporphyrins. Inorganic Chemistry 2017, 56 (18) , 11426-11434. https://doi.org/10.1021/acs.inorgchem.7b01946
    6. Timothy D. Lash . Carbaporphyrinoid Systems. Chemical Reviews 2017, 117 (4) , 2313-2446. https://doi.org/10.1021/acs.chemrev.6b00326
    7. Tamal Chatterjee, Vijayendra S. Shetti, Ritambhara Sharma, and Mangalampalli Ravikanth . Heteroatom-Containing Porphyrin Analogues. Chemical Reviews 2017, 117 (4) , 3254-3328. https://doi.org/10.1021/acs.chemrev.6b00496
    8. Leah M. Stateman and Timothy D. Lash . Syntheses of Carbaporphyrinoid Systems Using a Carbatripyrrin Methodology. Organic Letters 2015, 17 (18) , 4522-4525. https://doi.org/10.1021/acs.orglett.5b02219
    9. Stacy C. Fosu, Gregory M. Ferrence, and Timothy D. Lash . Synthesis and Metalation of Dimethoxybenziporphyrins, Thiabenziporphyrins, and Dibenziporphyrins. The Journal of Organic Chemistry 2014, 79 (22) , 11061-11074. https://doi.org/10.1021/jo502063w
    10. Deyaa I. AbuSalim, Gregory M. Ferrence, and Timothy D. Lash . Synthesis of an adj-Dicarbaporphyrin and the Formation of an Unprecedented Tripalladium Sandwich Complex. Journal of the American Chemical Society 2014, 136 (18) , 6763-6772. https://doi.org/10.1021/ja502795x
    11. David Tilly, Floris Chevallier, Florence Mongin, and Philippe C. Gros . Bimetallic Combinations for Dehalogenative Metalation Involving Organic Compounds. Chemical Reviews 2014, 114 (2) , 1207-1257. https://doi.org/10.1021/cr400367p
    12. Timothy D. Lash, Aaron D. Lammer, Aparna S. Idate, Denise A. Colby, and Kristen White . Preparation of Azulene-Derived Fulvenedialdehydes and Their Application to the Synthesis of Stable adj-Dicarbaporphyrinoids. The Journal of Organic Chemistry 2012, 77 (5) , 2368-2381. https://doi.org/10.1021/jo2026977
    13. Timothy D. Lash . Unexpected Alkyl Group Migration in Palladium(II) Benzocarbaporphyrins. Organic Letters 2011, 13 (17) , 4632-4635. https://doi.org/10.1021/ol2018483
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    15. Timothy D. Lash. Organometallic Chemistry within the Structured Environment Provided by the Macrocyclic Cores of Carbaporphyrins and Related Systems. Molecules 2023, 28 (3) , 1496. https://doi.org/10.3390/molecules28031496
    16. Timothy D. Lash. Recent developments in the chemistry of heteroporphyrins and heterocarbaporphyrins. 2022, 243-334. https://doi.org/10.1016/bs.aihch.2022.01.001
    17. Alexander Sadimenko. Pyrroles and benzannulated forms. 2020, 239-564. https://doi.org/10.1016/B978-0-08-102860-5.00003-1
    18. Tyler J. Smolczyk, Timothy D. Lash. Alphabet soup within a porphyrinoid cavity: synthesis of heterocarbaporphyrins with CNNO, CNOO, CNSO and CNSeO Cores from an oxacarbatripyrrin. Chemical Communications 2018, 54 (65) , 9003-9006. https://doi.org/10.1039/C8CC04976A
    19. Timothy D. Lash. What’s in a name? The MacDonald condensation. Journal of Porphyrins and Phthalocyanines 2016, 20 (08n11) , 855-888. https://doi.org/10.1142/S1088424616300147
    20. Timothy D. Lash, Deyaa I. AbuSalim, Gregory M. Ferrence. adj-Dicarbachlorin, the first free base carbaporphyrinoid system with an internal methylene unit. Chemical Communications 2015, 51 (88) , 15952-15955. https://doi.org/10.1039/C5CC06890H
    21. Timothy D. Lash. Metal Complexes of Carbaporphyrinoid Systems. Chemistry - An Asian Journal 2014, 9 (3) , 682-705. https://doi.org/10.1002/asia.201301594
    22. Yuequan Zhu, Min Zhang, Hongling Yuan, Yuefa Gong. Synthesis of functionalized fulvenes: [3 + 2] annulation of ethyl α-chlorocyclopropaneformates with 1,3-dicarbonyl compounds. Org. Biomol. Chem. 2014, 12 (44) , 8828-8831. https://doi.org/10.1039/C4OB01973C
    23. Regan D. Hartnell, Tomoki Yoneda, Hirotaka Mori, Atsuhiro Osuka, Dennis P. Arnold. The Marriage of Peripherally Metallated and Directly Linked Porphyrins: Bromidobis(phosphine)platinum(II) as a Cation‐Stabilizing Substituent on Directly Linked and Fused Triply Linked Diporphyrins. Chemistry – An Asian Journal 2013, 8 (11) , 2670-2679. https://doi.org/10.1002/asia.201300633
    24. Timothy D. Lash. Carbaporphyrins, porphyrin isomers and the legacy of Emanuel Vogel. Journal of Porphyrins and Phthalocyanines 2012, 16 (05n06) , 423-433. https://doi.org/10.1142/S1088424612300017
    25. Lili Sun, Guijuan Li, Qing Su. 3-[(2-Formylthiophen-3-yl)(hydroxy)methyl]thiophene-2-carbaldehyde. Acta Crystallographica Section E Structure Reports Online 2012, 68 (1) , o182-o182. https://doi.org/10.1107/S1600536811052500
    26. Timothy D. Lash. Origin of aromatic character in porphyrinoid systems. Journal of Porphyrins and Phthalocyanines 2011, 15 (11n12) , 1093-1115. https://doi.org/10.1142/S1088424611004063
    27. Lena Arnold, Klaus Müllen. Modifying the porphyrin core — a chemist's jigsaw. Journal of Porphyrins and Phthalocyanines 2011, 15 (09n10) , 757-779. https://doi.org/10.1142/S1088424611003720
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