Angewandte Chemie International Edition in English

Volume 19, Issue 2 pp. 143-145

Communication

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Synthesis and Transformations of 5-Cyano-2,2,8,8,12,13,17,18-octamethylisobacteriochlorin^†

Dr. Paul Naab,

Dr. Paul Naab

Chemisch-wissenschaftliches Laboratorium Bayer AG, D-5600 Wuppertal 1 (Germany)

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dipl.-Chem. ETH René Lattmann,

dipl.-Chem. ETH René Lattmann

Laboratorium für organische Chemie, Eidgenössische Technische Hochschule ETH-Zentrum, Universitätstrasse 16, CH-8092 Zürich (Switzerland)

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dipl.-Naturwiss. ETH Christof Angst,

dipl.-Naturwiss. ETH Christof Angst

Laboratorium für organische Chemie, Eidgenössische Technische Hochschule ETH-Zentrum, Universitätstrasse 16, CH-8092 Zürich (Switzerland)

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Prof. Dr. Albert Eschenmoser,

Corresponding Author

Prof. Dr. Albert Eschenmoser

Laboratorium für organische Chemie, Eidgenössische Technische Hochschule ETH-Zentrum, Universitätstrasse 16, CH-8092 Zürich (Switzerland)

Laboratorium für organische Chemie, Eidgenössische Technische Hochschule ETH-Zentrum, Universitätstrasse 16, CH-8092 Zürich (Switzerland)Search for more papers by this author

Dr. Paul Naab,

Dr. Paul Naab

Chemisch-wissenschaftliches Laboratorium Bayer AG, D-5600 Wuppertal 1 (Germany)

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dipl.-Chem. ETH René Lattmann,

dipl.-Chem. ETH René Lattmann

Laboratorium für organische Chemie, Eidgenössische Technische Hochschule ETH-Zentrum, Universitätstrasse 16, CH-8092 Zürich (Switzerland)

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dipl.-Naturwiss. ETH Christof Angst,

dipl.-Naturwiss. ETH Christof Angst

Laboratorium für organische Chemie, Eidgenössische Technische Hochschule ETH-Zentrum, Universitätstrasse 16, CH-8092 Zürich (Switzerland)

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Prof. Dr. Albert Eschenmoser,

Corresponding Author

Prof. Dr. Albert Eschenmoser

Laboratorium für organische Chemie, Eidgenössische Technische Hochschule ETH-Zentrum, Universitätstrasse 16, CH-8092 Zürich (Switzerland)

Laboratorium für organische Chemie, Eidgenössische Technische Hochschule ETH-Zentrum, Universitätstrasse 16, CH-8092 Zürich (Switzerland)Search for more papers by this author

First published: February 1980

https://doi.org/10.1002/anie.198001431

Citations: 24

^†

The Chemistry of Hexahydroporphyrins, Part 3. This work was supported by the Swiss National Science Foundation. P. N. (postdoctoral fellow at the ETH 1977/1978) gratefully acknowledges a scholarship from the German Science Foundation.—Part 2: [1b].

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A model substrate for studies in the hexahydroporphyrin series, i.e. the title compound (1) having C_2v symmetry, has been prepared by a multistep de-novo synthesis from a cyanosubstituted thiolactam. Catalytic hydrogenation of (1) affords the highly O₂-sensitive 2,3,7,8,15,24-hexahydro derivative; attempts to incorporate metal ions into this species lead to complexes of the 1,2,3,7,8,20-hexahydro isomer.

References

1(a) Ch. Angst, M. Kajiwara, E. Zass, A. Eschenmoser, Angew. Chem. 92, 139 (1980);
10.1002/ange.19800920226
CAS Google Scholar
Angew. Chem. Int. Ed. Engl. 19, 140 (1980);
10.1002/anie.198001401
Web of Science® Google Scholar
(b) J. E. Johansen, Ch. Angst, Ch. Kratky, A. Eschenmoser, Angew. Chem. Int. Ed. Engl. 92, 141 (1980) and
10.1002/ange.19800920227
CAS Web of Science® Google Scholar
Angew. Chem. Int. Ed. Engl. 19, 141 (1980), respectively;
10.1002/anie.198001411
CAS Web of Science® Google Scholar
(c) F.-P. Montforts, S. Ofner, V. Rasetti, A. Eschenmoser, W.-D. Woggon, K. Jones, A. R. Battersby, Angew. Chem. Int. Ed. Engl. 91, 752 (1979) and
10.1002/ange.19790910926
CAS Google Scholar
Angew. Chem. Int. Ed. Engl. 18, 675 (1979), respectively;
10.1002/anie.197906751
Web of Science® Google Scholar
(d) A. P. Johnson, P. Wehrli, R. Fletcher, A. Eschenmoser, Angew. Chem. Int. Ed. Engl. 80, 622 (1968) and
10.1002/ange.19680801518
Google Scholar
Angew. Chem. Int. Ed. Engl. 7, 623 (1968), respectively;
10.1002/anie.196806231
CAS Web of Science® Google Scholar
P. M. Müller. Diss. ETH No. 5135 Zürich, 1973.
Google Scholar
2 Prepared by chlorination of 3,3′,4,4′-tetramethylpyrromethene hydrochloride (S. Ofner, planned Dissertation, ETH Zürich) with chlorine in glacial acetic acid at RT, m.p. 180°C (decomp.). Preliminary experiments showed that the reaction sequence (6)→(8) works also with the dibromo-pyrromethene derivative described in [1c].
Google Scholar
3 Y. Yamada, D. Miljkovic, P. Wehrli, B. Golding, P. Löliger, R. Keese, K. Müller, A. Eschenmoser, Angew. Chem. 81, 301 (1969);
10.1002/ange.19690810902
Web of Science® Google Scholar
Angew. Chem. Int. Ed. Engl. 8, 343 (1969);
10.1002/anie.196903431
CAS PubMed Web of Science® Google Scholar
Dissertations, ETH Zürich: R. Scheffold, No. 3356, 1963;
Google Scholar
E. Bertele, No. 3357, 1963;
Google Scholar
P. Wehrli, No. 4043, 1967;
Google Scholar
H. J. Wild, No. 4848, 1972.
Google Scholar
4 M. Roth, P. Dubs, E. Götschi, A. Eschenmoser, Helv. Chim. Acta 54, 710 (1971);
10.1002/hlca.19710540229
CAS Web of Science® Google Scholar
E. Götschi, W. Hunkeler, H. J. Wild, P. Schneider, W. Fuhrer, J. Gleason, A. Eschenmoser, Angew. Chem. 85, 950 (1973);
10.1002/ange.19730852103
Google Scholar
Angew. Chem. Int. Ed. Engl. 12, 910 (1973).
10.1002/anie.197309101
CAS PubMed Web of Science® Google Scholar
5 E. Bertele, H. Boos, J. D. Dunitz, F. Elsinger, A. Eschenmoser, I. Felner, H. P. Gribi, H. Gschwend, E. F. Meyer, M. Pesaro, R. Scheffold, Angew. Chem. 76, 393 (1964);
10.1002/ange.19640761002
CAS Google Scholar
Angew. Chem. Int. Ed. Engl. 3, 490 (1964);
10.1002/anie.196404901
Web of Science® Google Scholar
A. Eschenmoser, Pure Appl. Chem. 20, 1 (1969);
10.1351/pac196920010001
CAS Google Scholar
Q. Rev. Chem. Soc. 24, 366 (1970).
10.1039/qr9702400366
CAS Web of Science® Google Scholar
6 Preliminary experiments to prepare (6) via the iminoester/enamine condensation, and experiments on the condensation of the thiomethyl iminoester derived from (1) with lithium tert-butyl acetate (cf. [1c]) failed.
Google Scholar
7 On access of air (10) is immediately oxidized to (8); cf. the UV/VIS spectrum of (10) in Table 1.
Google Scholar
8 The UV/VIS-spectrum of (12) corresponds to the spectra of the nickel(II) octaethyl-1,2,3,7,8,20-hexahydroporphyrinates described in [1b] (X-ray analyses!).
Google Scholar
9 Plus 2% (11).—Partial disproportionation of (10) was also observed under various reaction conditions (e.g. with acids other than formic acid) [11].
Google Scholar
10 For the exclusion of oxygen in these experiments cf. note [5] in [1a].
Google Scholar
11 For experimental details, cf. R. Lattmann, planned Dissertation, ETH Zürich.
Google Scholar
12 1,8-Diazabicyclo[5.4.0]undec-7-ene ( H. Oediger, F. Möller, K. Eiter, Synthesis 1972, 591).
10.1055/s-1972-21943
CAS Google Scholar
13 Yield of (6) after crystallization: 55%. The mother liquors were reconverted to (5) with KCN in DMF (60°C); yield of (6) based on reacted starting material: 92%.
Google Scholar

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Volume19, Issue2

February 1980

Pages 143-145

Synthesis and Transformations of 5-Cyano-2,2,8,8,12,13,17,18-octamethylisobacteriochlorin^†

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Synthesis and Transformations of 5-Cyano-2,2,8,8,12,13,17,18-octamethylisobacteriochlorin†

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Synthesis and Transformations of 5-Cyano-2,2,8,8,12,13,17,18-octamethylisobacteriochlorin^†