A Variation of the Sulfide Contraction Procedure for Synthesis of Corrinoid Systems
1973; Wiley; Volume: 12; Issue: 11 Linguagem: Inglês
10.1002/anie.197309101
ISSN1521-3773
AutoresErwin Götschi, Walter Hunkeler, Hans‐Jakob Wild, Peter Schneider, Walter Fuhrer, John G. Gleason, Albert Eschenmoser,
Tópico(s)History and advancements in chemistry
ResumoAngewandte Chemie International Edition in EnglishVolume 12, Issue 11 p. 910-912 Communication A Variation of the Sulfide Contraction Procedure for Synthesis of Corrinoid Systems† dipl. Naturwissenschafter ETH-Z Erwin Götschi, dipl. Naturwissenschafter ETH-Z Erwin Götschi Organisch-Chemisches Laboratorium der Eidgenössischen Technischen Hochschule, CH-8006 Zürich, Universitätsstrasse 6 (Switzerland)Search for more papers by this authorDr. Walter Hunkeler, Dr. Walter Hunkeler Organisch-Chemisches Laboratorium der Eidgenössischen Technischen Hochschule, CH-8006 Zürich, Universitätsstrasse 6 (Switzerland)Search for more papers by this authorDipl. Ing.-Chem. ETH-Z Hans-Jakob Wild, Dipl. Ing.-Chem. ETH-Z Hans-Jakob Wild Organisch-Chemisches Laboratorium der Eidgenössischen Technischen Hochschule, CH-8006 Zürich, Universitätsstrasse 6 (Switzerland)Search for more papers by this authorDipl. Ing.-Chem. ETH-Z Peter Schneider, Dipl. Ing.-Chem. ETH-Z Peter Schneider Organisch-Chemisches Laboratorium der Eidgenössischen Technischen Hochschule, CH-8006 Zürich, Universitätsstrasse 6 (Switzerland)Search for more papers by this authordipl. Naturwissenschafter ETH-Z Walter Fuhrer, dipl. Naturwissenschafter ETH-Z Walter Fuhrer Organisch-Chemisches Laboratorium der Eidgenössischen Technischen Hochschule, CH-8006 Zürich, Universitätsstrasse 6 (Switzerland)Search for more papers by this authorDr. John Gleason, Dr. John Gleason Organisch-Chemisches Laboratorium der Eidgenössischen Technischen Hochschule, CH-8006 Zürich, Universitätsstrasse 6 (Switzerland)Search for more papers by this authorProf. Dr. Albert Eschenmoser, Corresponding Author Prof. Dr. Albert Eschenmoser Organisch-Chemisches Laboratorium der Eidgenössischen Technischen Hochschule, CH-8006 Zürich, Universitätsstrasse 6 (Switzerland)Organisch-Chemisches Laboratorium der Eidgenössischen Technischen Hochschule, CH-8006 Zürich, Universitätssstrasse 6 (Switzerland)Search for more papers by this author dipl. Naturwissenschafter ETH-Z Erwin Götschi, dipl. Naturwissenschafter ETH-Z Erwin Götschi Organisch-Chemisches Laboratorium der Eidgenössischen Technischen Hochschule, CH-8006 Zürich, Universitätsstrasse 6 (Switzerland)Search for more papers by this authorDr. Walter Hunkeler, Dr. Walter Hunkeler Organisch-Chemisches Laboratorium der Eidgenössischen Technischen Hochschule, CH-8006 Zürich, Universitätsstrasse 6 (Switzerland)Search for more papers by this authorDipl. Ing.-Chem. ETH-Z Hans-Jakob Wild, Dipl. Ing.-Chem. ETH-Z Hans-Jakob Wild Organisch-Chemisches Laboratorium der Eidgenössischen Technischen Hochschule, CH-8006 Zürich, Universitätsstrasse 6 (Switzerland)Search for more papers by this authorDipl. Ing.-Chem. ETH-Z Peter Schneider, Dipl. Ing.-Chem. ETH-Z Peter Schneider Organisch-Chemisches Laboratorium der Eidgenössischen Technischen Hochschule, CH-8006 Zürich, Universitätsstrasse 6 (Switzerland)Search for more papers by this authordipl. Naturwissenschafter ETH-Z Walter Fuhrer, dipl. Naturwissenschafter ETH-Z Walter Fuhrer Organisch-Chemisches Laboratorium der Eidgenössischen Technischen Hochschule, CH-8006 Zürich, Universitätsstrasse 6 (Switzerland)Search for more papers by this authorDr. John Gleason, Dr. John Gleason Organisch-Chemisches Laboratorium der Eidgenössischen Technischen Hochschule, CH-8006 Zürich, Universitätsstrasse 6 (Switzerland)Search for more papers by this authorProf. Dr. Albert Eschenmoser, Corresponding Author Prof. Dr. Albert Eschenmoser Organisch-Chemisches Laboratorium der Eidgenössischen Technischen Hochschule, CH-8006 Zürich, Universitätsstrasse 6 (Switzerland)Organisch-Chemisches Laboratorium der Eidgenössischen Technischen Hochschule, CH-8006 Zürich, Universitätssstrasse 6 (Switzerland)Search for more papers by this author First published: November 1973 https://doi.org/10.1002/anie.197309101Citations: 42 † This work was supported by the Schweizerischer Nationalfonds zur Förderung der wissenschaftlichen Forschung. AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat References 1 A. Eschenmoser, Quart. Rev. Chem. Soc. 24, 366 (1970); 10.1039/qr9702400366 CASWeb of Science®Google Scholar Pure. Appl. Chem. Suppl. XXIII IUPAC Congress, Boston, Vol. 2, 69 (1971); Google Scholar R. B. Woodward, Pure Appl. Chem. 17, 519 (1968); 10.1351/pac196817030519 CASPubMedGoogle Scholar Pure. Appl. Chem. 25, 283 (1971); 10.1351/pac197125010283 CASPubMedGoogle Scholar Pure. Appl. Chem. 33, 145 (1973). 10.1351/pac197333010145 CASPubMedGoogle Scholar 2 Y. Yamada, D. Miljkovic, P. Wehrli, B. Golding, P. Löliger, R. Keese, K. Müller, and A. Eschenmoser, Angew. Chem. 81, 301 (1969); 10.1002/ange.19690810902 Google Scholar Angew. Chem. internat. Edit. 8, 343 (1969). 10.1002/anie.196903431 CASPubMedGoogle Scholar 3 A. Fischli and A. Eschenmoser, Angew. Chem. 79, 865 (1967); 10.1002/ange.19670791913 Google Scholar Angew. Chem. internat. Edit. 6, 866 (1967). 10.1002/anie.196708661 CASPubMedWeb of Science®Google Scholar 4 M. Roth, P. Dubs, E. Götschi, and A. Eschenmoser, Helv. Chim. Acta 54, 710 (1971). 10.1002/hlca.19710540229 CASWeb of Science®Google Scholar 5 G. Traverso, A. Barco, G. P. Pollini, M. Anastasia, V. Sticchi, and D. Pirillo, Farmaco Ed. Sci. 24, 946 (1969); CASPubMedWeb of Science®Google Scholar G. Traverso, A. Barco, and G. P. Pollini, Chem. Commun. 1971, 326; Google Scholar G. Traverso, G. P. Pollini, A. Barco, and G. De Giuli, Gazz. Chim. Ital. 102, 243 (1972). CASWeb of Science®Google Scholar 6 R. V. Stevens, L. E. Du Pree jun., and M. P. Wentland, Chem. Commun. 1970, 821; Google Scholar R. V. Stevens, C. G. Christensen, W. L. Edmonson, M. Kaplan, E. B. Reid, and M. P. Wentland, J. Amer. Chem. Soc. 93, 6229 (1971); Google Scholar R. V. Stevens, L. E. Du Pree jun., W. L. Edmonson, L. L. Magid, and M. P. Wentland, J. Amer. Chem. Soc. 93, 6637 (1971). 10.1021/ja00753a051 CASWeb of Science®Google Scholar 7 A. W. Johnson and W. R. Overend, Chem. Commun. 1971, 710; Google Scholar J. C. S. Perkin I 1972, 2681; Google Scholar cf. also H. H. Inhoffen, J. Ulrich, H. A. Hoffmann, and G. Klinzmann, Tetrahedron Lett. 1969, 613. Google Scholar 8 B. Golding and P. Löliger; cf. P. Löliger, Dissertation, ETH Zürich 1968. Google Scholar 9 For the development of this procedure in the synthesis of vitamin B12 see [1], also P. Schneider, Dissertation, ETH, Zürich 1972, and W. Fuhrer, Dissertation, ETH Zürich, 1973. Google Scholar 10 E. Bertele, H. Boos, J. D. Dunitz, F. Elsinger, A. Eschenmoser, I. Felner, H. P. Gribi, H. GsChwend, E. F. Meyer, M. Pesaro, and R. Scheffold, Angew. Chem. 76, 393 (1964); 10.1002/ange.19640761002 CASGoogle Scholar Angew. Chem. internat. Edit. 3, 490 (1964). 10.1002/anie.196404901 Web of Science®Google Scholar 11 H.-J. Wild, Dissertation, ETH Zürich 1972. Google Scholar 12 E. Götschi, Dissertation, ETH Zürich 1973. Google Scholar 13 Iodination of (2a) with 1.0 equiv. of I2 in ether in presence of solid K2CO3 at room temperature affords 87% of (2b), m.p. 88°C, λmax = 238 nm (ε = 14200) in C2H5OH; δ = 1.30 (s, 2CH3), 2.50 (s, CH2), 4.93 (s, CH), 7.6 (br., NH) ppm in CDCl3; ṽNH in CCl4 at c ≤ 6 6 × 10−3 mol/l = 3410 cm−1( sharp, no intermolecular H-bonding). Iodination of (2a) with 2.0 equiv of I2 affords the diiodide, m.p. 144°C; δ (CH3) = 1.58 ṽNH in CCl4 at c ≤ 6.6 × 10−3 mol/l = 3395 cm−1 (sharp) Reduction of the diiodide with (C6H5)3SnH/pyridine in CDCl3 at 45°C gives, along with (2b), the (NH/I)- trans-monoiodide, m.p. 105°C, λmax = 240 nm (ε = 18700); δ = 1.54 (s, 2CH3), 2.47 (s, CH2), 5.24 (s, CH), 8.7 (br., NH) ppm; ṽNH in CCl4, at c ≥ 6.6 × 10−3 mol/l = 3430 (sharp) and 3170 (br.) cm−1 (concentration-dependent, intermolecular H-bonding). This trans-monoiodide isomerizes very rapidly and completely into (2b) on contact with acids or bases. Google Scholar 14 Cf. E. Götschi and A. Eschenmoser, Angew. Chem. 85, 952 (1973); 10.1002/ange.19730852104 Google Scholar Angew. Chem. internat. Edit. 12, 912 (1973). 10.1002/anie.197309121 CASPubMedWeb of Science®Google Scholar 15 Prepared by treatment of (6) [10, 2, 5, 6] with iodosuccinimide in benzene/(CH3)3COH at room temperature for 30 min; yield 81% [12]. The physical data for (7) are given in [14]. Google Scholar 16 It is possible to obtain this coupling product from the bisimidoyl disulfide produced from (5) by benzoyl peroxide, but that method is preparatively unsatisfactory; cf. P. Wehrli, Dissertation, ETH, Zürich 1967. Google Scholar 17 Cf. P. Müller, S. Farooq, B. Hardegger, W. Salmond, and A. Eschenmoser, Angew. Chem. 85, 954 (1973); 10.1002/ange.19730852105 CASGoogle Scholar Angew. Chem. internat. Edit. 12, 914 (1973). Data for (9) are given therein 10.1002/anie.197309141 Web of Science®Google Scholar 18 Under such reaction conditions, at most ca. 5% of the iodine of (2b) is transferred to (14) [NMR spectroscopic D-analysis of recovered (2b) in a control experiment without (1a)]. Deuterium in the position a to the lactam group of (2a), unlike that in the vinyl position, is resistant to exchange under the reaction conditions. Detailed descriptions of the experiments referring to the mechanism of the coupling reaction are given by E. Götschi [12]. Google Scholar Citing Literature Volume12, Issue11November 1973Pages 910-912 ReferencesRelatedInformation
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