Research Article

Reactions of the HCN-Tetramer with Aldehydes^†

Klemens Koch

Laboratory of Organic Chemistry, Swiss Federal Institute of Technology (ETH), Hönggerberg HCI, Wolfgang-Pauli-Strasse 10, CH-8093 Zürich

Dorfstrasse 13, CH-2572 Sutz. The work described here is one of the four parts of the thesis: Klemens Koch, Promotionsarbeit ETH-Zürich, 1989–1992 [2] (Chapt. 3: ‘Die aldehydkatalysierte Hydratisierung von Blausäure-Oligomeren’, p. 33–61); the full text of the thesis can be downloaded from the internet: http://e-collection.ethbib.ethz.ch/show?type=diss&nr=9968.

Search for more papers by this author

W. Bernd Schweizer,

W. Bernd Schweizer

Laboratory of Organic Chemistry, Swiss Federal Institute of Technology (ETH), Hönggerberg HCI, Wolfgang-Pauli-Strasse 10, CH-8093 Zürich

Search for more papers by this author

Albert Eschenmoser,

Albert Eschenmoser

[email protected]

Laboratory of Organic Chemistry, Swiss Federal Institute of Technology (ETH), Hönggerberg HCI, Wolfgang-Pauli-Strasse 10, CH-8093 Zürich

Search for more papers by this author

Klemens Koch,

Klemens Koch

Laboratory of Organic Chemistry, Swiss Federal Institute of Technology (ETH), Hönggerberg HCI, Wolfgang-Pauli-Strasse 10, CH-8093 Zürich

Search for more papers by this author

W. Bernd Schweizer,

W. Bernd Schweizer

Laboratory of Organic Chemistry, Swiss Federal Institute of Technology (ETH), Hönggerberg HCI, Wolfgang-Pauli-Strasse 10, CH-8093 Zürich

Search for more papers by this author

Albert Eschenmoser,

Albert Eschenmoser

[email protected]

Laboratory of Organic Chemistry, Swiss Federal Institute of Technology (ETH), Hönggerberg HCI, Wolfgang-Pauli-Strasse 10, CH-8093 Zürich

Search for more papers by this author

First published: 19 April 2007

https://doi.org/10.1002/cbdv.200790049

Citations: 18

^†

Chemistry of α-Aminonitriles Part 47. For part 46, see [1].

About

PDF

Tools

Share a link

Email
Wechat
Bluesky

Abstract

The HCN-tetramer, a ‘classic’ of the prebiotic chemistry of HCN, is shown to undergo a remarkable reaction with acetaldehyde in slightly basic or neutral aqueous solution at room temperature. The reaction consists in an aldolization-type C,C-bond formation, accompanied by a (presumably aldehyde-catalyzed) hydration of one of the two nitrile groups and the formation of two cyclic aminal-type groupings, each of the latter incorporating an additional molecule of the aldehyde. Should this so far unexplored type of chemistry of the HCN-tetramer prove to have some generality, the finding might add a new dimension to the potential etiological relevance of this HCN-oligomer.

References

1 G. K. Mittapalli, Y. Osornio, M. Guerrero, K. R. Reddy, R. Krishnamurthy, A. Eschenmoser, Angew. Chem., Int. Ed. 2007, 46, 2478.
10.1002/anie.200603209
CAS PubMed Web of Science® Google Scholar
2 K. Koch, ‘Über strukturelle Zusammenhänge zwischen Blausäure und natürlichen Purinen und Pteridinen’, Ph.D. Thesis No. 9968, ETH Zürich, Zürich, 1992; http://e-collection.ethbib.ethz.ch/show?type=diss&nr=9968.
Google Scholar
3 G. Ksander, G. Bold, R. Lattmann, C. Lehmann, T. Frueh, Y.-B. Xiang, K. Inomata, H. P. Buser, J. Schreiber, E. Zass, A. Eschenmoser, Helv. Chim. Acta 1987, 70, 1115;
10.1002/hlca.19870700424
CAS Web of Science® Google Scholar
S. Drenkard, J. Ferris, A. Eschenmoser, Helv. Chim. Acta 1990, 73, 1373;
10.1002/hlca.19900730524
CAS PubMed Web of Science® Google Scholar
E. Wagner, Y.-B. Xiang, K. Baumann, J. Gück, A. Eschenmoser, Helv. Chim. Acta 1990, 73, 1391;
10.1002/hlca.19900730525
CAS Web of Science® Google Scholar
D. Müller, S. Pitsch, A. Kittaka, E. Wagner, C. E. Wintner, A. Eschenmoser, Helv. Chim. Acta 1990, 73, 1410;
10.1002/hlca.19900730526
CAS Web of Science® Google Scholar
Y.-B. Xiang, S. Drenkard, K. Baumann, D. Hickey, A. Eschenmoser, Helv. Chim. Acta 1994, 77, 2209;
10.1002/hlca.19940770814
CAS Web of Science® Google Scholar
S. Pitsch, E. Pombo-Villar, A. Eschenmoser, Helv. Chim. Acta 1994, 77, 2251.
10.1002/hlca.19940770815
CAS Web of Science® Google Scholar
4 R. Pascal, J. Taillades, A. Commeyras, Bull. Soc. Chim. Fr. 1978, II-177;
Google Scholar
R. Pascal, J. Taillades, A. Commeyras, Tetrahedron 1979, 34, 2275;
10.1016/0040-4020(78)89038-3
Web of Science® Google Scholar
J. T. Edward, F. L. Chubb, Proc. R. Ir. Acad. 1983, 83, 57;
Web of Science® Google Scholar
R. Pascal, Eur. J. Org. Chem. 2003, 1813.
10.1002/ejoc.200200530
CAS Web of Science® Google Scholar
5 K. U. Schoening, P. Scholz, S. Guntha, X. Wu, R. Krishnamurthy, A. Eschenmoser, Science 2000, 290, 1347;
10.1126/science.290.5495.1347
PubMed Web of Science® Google Scholar
K. U. Schoening, P. Scholz, X. Wu, S. Guntha, G. Delgado, R. Krishnamurthy, A. Eschenmoser, Helv. Chim. Acta 2002, 85, 4111.
10.1002/hlca.200290000
Web of Science® Google Scholar
6 A. Eschenmoser, Orig. Life Evol. Biosphere 2004, 34, 277.
10.1023/B:ORIG.0000016450.59665.f4
CAS PubMed Web of Science® Google Scholar
7 R. A. Sanchez, J. P. Ferris, L. E. Orgel, J. Mol. Biol. 1967, 30, 223.
CAS PubMed Web of Science® Google Scholar
8 S. L. Miller, L. E. Orgel, ‘The Origins of Life on the Earth’, Prentice-Hall, Englewood Cliffs, 1974;
Google Scholar
J. P. Ferris, W. J. Hagan Jr., Tetrahedron 1984, 40, 1093.
10.1016/S0040-4020(01)99315-9
CAS PubMed Web of Science® Google Scholar
9 J. P. Ferris, E. H. Edelson, J. Org. Chem. 1978, 43, 3989.
10.1021/jo00415a001
Web of Science® Google Scholar
10 G. M. Sheldrick, SHELX76, Program for Crystal Structure Determination, University of Cambridge, Cambridge, UK, 1976;
Google Scholar
G. M. Sheldrick, SHELX86, Program for the Solution of Crystal Structures, University of Göttingen, Göttingen, 1985.
Google Scholar
11 J. W. Thanassi, J. Org. Chem. 1975, 40, 2678.
10.1021/jo00906a023
CAS Web of Science® Google Scholar
12 J. Selambarom, F. Carre, A. Fruchier, J. P. Roque, A. A. Pavia, Tetrahedron 2002, 58, 4439.
10.1016/S0040-4020(02)00405-2
CAS Web of Science® Google Scholar
13 R. W. Begland, D. R. Hartter, F. N. Jones, D. J. Sam, W. A. Sheppard, O. W. Webster, F. J. Weigert, J. Org. Chem. 1974, 39, 2341;
10.1021/jo00930a004
CAS Web of Science® Google Scholar
P. S. Robertson, J. Vaughan, J. Am. Chem. Soc. 1958, 80, 2691.
10.1021/ja01544a026
CAS Web of Science® Google Scholar
14 Y. Ohtsuka, J. Org. Chem. 1978, 43, 3231;
10.1021/jo00410a027
CAS Web of Science® Google Scholar
Y. Ohtsuka, J. Org. Chem. 1979, 44, 827;
10.1021/jo01319a036
CAS Web of Science® Google Scholar
Y. Ohtsuka, E. Thoma, S. Kojima, N. Tomita, J. Org. Chem. 1979, 44, 4871.
10.1021/jo00394a027
CAS Web of Science® Google Scholar
15 A. Eschenmoser, Chem. Biodiv. 2007, 4, 554.
10.1002/cbdv.200790050
CAS PubMed Web of Science® Google Scholar

Citing Literature

Volume4, Issue4

April 2007

Pages 541-553

Reactions of the HCN-Tetramer with Aldehydes^†

Abstract

References

Citing Literature

References

Information

About Wiley Online Library

Help & Support

Opportunities

Connect with Wiley

Reactions of the HCN-Tetramer with Aldehydes†

Abstract

References

Citing Literature

References

Related

Information

Reactions of the HCN-Tetramer with Aldehydes^†