Cyanide-Catalyzed Cyclizations via Aldimine Coupling

Journal of Organic Chemistry

Volumn 69, Issue 4, 2004, Pages 1357-1359

  Reich, B Jesse E ^a   Justice, Aaron K ^a   Beckstead, Brittany T ^a   Reibenspies, Joseph H ^a   Miller, Stephen A ^a  

^a TEXAS A AND M UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CATALYSIS; CONDENSATION; METHANOL; OXIDATION; SODIUM COMPOUNDS;

ALDIMINE COUPLINGS (AIC); CYCLIZATIONS;

CYANIDES;

ALDEHYDE; AMINE; BENZOIN; CYANIDE; DIAMINE; DICHLOROMETHANE; DIKETONE; HETEROCYCLIC COMPOUND; IMINE; METHANOL; N,N DIMETHYLFORMAMIDE; NITROGEN DERIVATIVE; PYRAZINE DERIVATIVE; QUINOXALINE DERIVATIVE; SCHIFF BASE; SODIUM CYANIDE; VANILLIN; WATER;

ARTICLE; CATALYST; CYCLIZATION; DIMERIZATION; HYDROGEN BOND; OLIGOMERIZATION; OXIDATION; POLYMERIZATION; REACTION ANALYSIS; TEMPERATURE; X RAY CRYSTALLOGRAPHY;

EID: 1242329845     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo035245j     Document Type: Article

References (31)

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18. The benzoin condensation is technically a dimerization since the molecular weight of benzoin is twice that of benzaldehyde. Hence, the term "coupling" is introduced to avoid the misleading descriptor "condensation", and is meant to apply generally to intermolecular and intramolecular reactions.
19. For recent examples of intramolecular benzoin condensations (dialdehyde substrates) see: Modler-Spreitzer, A.; Fritsch, R.; Mannschreck, A. Collect. Czech. Chem. Commun. 2000, 65, 555-560. Yang, Z.; Wong, H. N. C.; Hon, P. M.; Chang, H. M.; Lee, C. M. J. Org. Chem. 1992, 57, 4033-4034. Intramolecular cyclization of aldehyde-ketone substrates has recently been reported: Hachisu, Y.; Bode, J. W.; Suzuki, K. J. Am. Chem. Soc. 2003, 125, 8432-8433.
20. For recent examples of intramolecular benzoin condensations (dialdehyde substrates) see: Modler-Spreitzer, A.; Fritsch, R.; Mannschreck, A. Collect. Czech. Chem. Commun. 2000, 65, 555-560. Yang, Z.; Wong, H. N. C.; Hon, P. M.; Chang, H. M.; Lee, C. M. J. Org. Chem. 1992, 57, 4033-4034. Intramolecular cyclization of aldehyde-ketone substrates has recently been reported: Hachisu, Y.; Bode, J. W.; Suzuki, K. J. Am. Chem. Soc. 2003, 125, 8432-8433.
21. For recent examples of intramolecular benzoin condensations (dialdehyde substrates) see: Modler-Spreitzer, A.; Fritsch, R.; Mannschreck, A. Collect. Czech. Chem. Commun. 2000, 65, 555-560. Yang, Z.; Wong, H. N. C.; Hon, P. M.; Chang, H. M.; Lee, C. M. J. Org. Chem. 1992, 57, 4033-4034. Intramolecular cyclization of aldehyde-ketone substrates has recently been reported: Hachisu, Y.; Bode, J. W.; Suzuki, K. J. Am. Chem. Soc. 2003, 125, 8432-8433.
22. 2) = 0.1569, GOF = 1.089 for 184 parameters and 2189 unique data.
23. 2) = 0.1430, GOF = 1.091 for 225 parameters and 2472 unique data.
24. 4. Filtration and in vacuo drying afforded 7.00 g (87.5%) of the product as a yellow powder. See the Supporting Information for full synthetic details.
25. Extreme caution should always be taken when handling any form of cyanide. All reactions should be conducted in a well-ventilated fume hood and one should avoid the addition of acid during workup as this evolves HCN. The products reported herein were conveniently isolated by filtration as crystalline solids from which NaCN readily washed away.
26. Quinoxaline from Scheme 2: (a) Tanaka, S.; Yokoyama, K.; Takashima, M. Japanese Patent 40,012,294, 1965.
27. Quinoxaline from entry 2: (b) Bost, R. W.; Towell, E. E. J. Am. Chem. Soc. 1948, 70, 903-905.
28. Pyrazine from entry 3: (c) Jimeno, M. L.; de Paz, J. L. G.; Rodriguez, J.; Rodriguez, M.; Ochoa, C. Anal. Quim. 1994, 90 (7-8), 423-431.
29. Pearl, I. A. J. Am. Chem. Soc. 1952, 74, 4620-4662.
30. An X-ray crystallographic study (see the Supporting Information) clearly shows the imine-amine tautomer of the heterocycle from entry 6-not the alternative ene-diamine tautomer described in eq 2. The imine-amine tautomer is stabilized by a single intramolecular hydrogen bond in the solid state (N ⋯ H = 1.35 Å).
31. 1H NMR end-group analysis indicates an average degree of polymerization of 4.34. While the monomer is colorless, the oligomeric product exhibits an orange-red coloration indicative of a long, conjugated system.