One-carbon extrusion from a tetraazafulvalene. Isolation of aldehydes and a study of their origin

Journal of the American Chemical Society

Volumn 131, Issue 18, 2009, Pages 6475-6479

  Murphy, John A ^a   Schoenebeck, Franziska ^a   Findlay, Neil J ^a   Thomson, Douglas W ^a   Zhou, Sheng Ze ^a   Garnier, Jean ^a  

^a UNIVERSITY OF STRATHCLYDE   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

ALIPHATIC ALDEHYDES; ALKYL GROUPS; ARYL IODIDES; CARBON EXTRUSION; IMIDAZOLINES; IMIDAZOLYLIDENE; IN-SITU; ONE-CARBON UNITS; SIDE CHAINS;

BROMINE COMPOUNDS; EXTRUSION; OLEFINS; SUBSTRATES;

ALDEHYDES;

ALDEHYDE DERIVATIVE; ALIPHATIC COMPOUND; ALKENE DERIVATIVE; AMINE; BROMINE DERIVATIVE; CARBON; IMIDAZOLE DERIVATIVE; IMIDAZOLINE DERIVATIVE; IODINE DERIVATIVE; TETRAAZAFULVALENE; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL REACTION; NUCLEAR MAGNETIC RESONANCE;

EID: 70149102657     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja8092746     Document Type: Article

References (28)

1. Among very recent reviews, see (a) Diez-Gonzalez, S.; Nolan, S. P. Aldrichim. Acta 2008, 41, 43-51.
2. Lewis, J. C.; Bergman, R. G.; Ellman, J. A. Acc. Chem. Res. 2008, 41, 1013-1025.
3. Raubenheimer, H. G.; Cronje, S. Chem. Soc. Rev. 2008, 37, 1998-2011.
4. Herrmann, W. A.; Schutz, J.; Frey, G. D.; Herdtweck, E. Organometallics 2006, 25, 2437-2448.
5. Marion, N.; Diez-Gonzalez, S.; Nolan, I. P. Angew. Chem., Int. Ed. 2007, 46, 2988-3000.
6. Enders, D.; Balensiefer, T. Acc. Chem. Res. 2004, 37, 534-541.
7. Suzuki, Y. J. Synth. Org. Chem. Jpn. 2008, 66, 377-386.
8. Rovis, T. Chem. Lett. 2008, 37, 2-7.
9. For reviews, see (a) Alder, R. W.; Blake, M. E.; Chaker, L.; Harvey, J. N.; Schütz, J. Angew. Chem., Int. Ed. 2004, 43, 5896-5911.
10. Hahn, F. E.; Jahnke, M. C. Angew. Chem., Int. Ed. 2008, 47, 3122-3172.
11. Lappert, M. F. J. Organomet. Chem. 2005, 690, 5467-5473.
12. Murphy, J. A.; Khan, T. A.; Zhou, S.-Z.; Thomson, D. W.; Mahesh, M. Angew. Chem., Int. Ed. 2005, 44, 1356-1360.
13. Ames, J. R.; Houghtaling, M. A.; Terrian, D. L.; Mitchell, T. A. Can. J. Chem. 1997, 75, 28-36.
14. Molander, G. A.; Harris, C. R. J. Org. Chem. 1998, 63, 4374-4380.
15. Concellon, J. M.; Bernad, P. L.; Perez-Andres, J. A. Angew. Chem., Int. Ed. 1999, 38, 2384-2386.
16. For previous preparation of molecule 2, see Taton, T. A.; Chen, P. Angew. Chem., Int. Ed. Engl. 1996, 35, 1011-1013.
17. Murphy, J. A.; Zhou, S.-Z.; Thomson, D. W.; Schoenebeck, F.; Mahesh, M.; Park, S. R.; Tuttle, T.; Berlouis, L. E. A. Angew. Chem., Int. Ed. 2007, 46, 5178-5183.
18. Schoenebeck, F.; Murphy, J. A.; Zhou, S. Z.; Uenoyama, Y.; Miclo, Y.; Tuttle, T. J. Am. Chem. Soc. 2007, 129, 13368-13369.
19. 1/2=-1.20 V in DMF5. All values are relative to saturated calomel electrode (SCE).
20. For discussion of very strong neutral organic electron donors, see (a) Porter, W. W., III; Vaid, T. P.; Rheingold, A. L. J. Am. Chem. Soc. 2005, 127, 16559-16566.
21. Murphy, J. A.; Garnier, J.; Park, S. R.; Schoenebeck, F.; Zhou, S.-Z.; Turner, A. T. Org. Lett. 2008, 10, 1227-1230.
22. Garnier, J.; Murphy, J. A.; Zhou, S.-Z.; Turner, A. T. Synlett 2008, 2127-2131.
23. Cutulic, S. P. Y.; Murphy, J. A.; Farwaha, H.; Zhou, S.-Z.; Chrystal, E. Synlett 2008, 2132-2136.
24. Burkholder, C.; Dolbier, W. R., Jr.; Médebielle, M. J. Org. Chem. 1998, 63, 5385-5394.
25. Aldehydes had not been seen when these substrates were reacted with 1.
26. See (a) p 5906, in ref 3a;
27. p 3137 in ref 3b. Our calculations (B3LYP/6-31G*) indicate that 25 is favoured in an equilibrium with 24; ΔGrxn)-2.6 kcal/mol (gas phase) for the conversion of 24 to 25 (with R ) Me). Gaussian03 was used for this calculation. [Gaussian03, Revision C.02, M. J. Frisch et al. See Supporting Information for full reference.]
28. Although there are a few examples of cyclization of aryl anions onto unactivated pendant alkenes, such reactions have only been achieved in the absence of electrophiles. See Ross, G. A.; Koppang, M. D.; Bartak, D. E.; Woolsey, N. F. J. Am. Chem. Soc. 1985, 107, 6742-6743.