Visible light-mediated intermolecular C-H functionalization of electron-rich heterocycles with malonates

Organic Letters

Volumn 12, Issue 13, 2010, Pages 3104-3107

  Furst, Laura ^a   Matsuura, Bryan S ^a   Narayanam, Jagan M R ^a   Tucker, Joseph W ^a   Stephenson, Corey R J ^a  

^a Boston University   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

FURAN DERIVATIVE; HETEROCYCLIC COMPOUND; INDOLE DERIVATIVE; MALONIC ACID DERIVATIVE; PYRROLE DERIVATIVE;

ARTICLE; CHEMICAL STRUCTURE; CHEMISTRY; ELECTRON; LIGHT; OXIDATION REDUCTION REACTION; PHOTOCHEMISTRY; STEREOISOMERISM;

ELECTRONS; FURANS; HETEROCYCLIC COMPOUNDS; INDOLES; LIGHT; MALONATES; MOLECULAR STRUCTURE; OXIDATION-REDUCTION; PHOTOCHEMISTRY; PYRROLES; STEREOISOMERISM;

EID: 77954133344     PISSN: 15237060     EISSN: 15237052     Source Type: Journal    
DOI: 10.1021/ol101146f     Document Type: Article

References (34)

1. For an excellent review, see: Johansson, C. C. C.; Colacot, T. J. Angew. Chem., Int. Ed. 2010, 49, 676
2. Kawatsura, M.; Hartwig, J. F. J. Am. Chem. Soc. 1999, 121, 1473
3. For selected recent examples, see
4. Yip, S. F.; Cheung, H. Y.; Zhou, Z.; Kwong, F. Y. Org. Lett. 2007, 9, 3469
5. Hama, T.; Hartwig, J. F. Org. Lett. 2008, 10, 1545
6. Dai, X.; Strotman, N. A.; Fu, G. C. J. Am. Chem. Soc. 2008, 130, 3302
7. For selected examples of the functionalization of indoles and pyrroles, see
8. Tsai, A.-I.; Lin, C.-H.; Chuang, C.-P. Heterocycles 2005, 65, 2381
9. Richter, J. M.; Whitefield, B. W.; Maimone, T. J.; Lin, D. W.; Castroviejo, M. P.; Baran, P. S. J. Am. Chem. Soc. 2007, 129, 12857
10. Antos, J. M.; McFarland, J. M.; Iavarone, A. T.; Francis, M. B. J. Am. Chem. Soc. 2009, 131, 6301
11. Chan, W.-W.; Yeung, S.-H.; Zhou, Z.; Chan, A. S. C.; Yu, W. Y. Org. Lett. 2010, 12, 604
12. 3 as the initiator in combination with excess of arene (5-15 equiv). See: Byers, J. H.; Campbell, J. E.; Knapp, F. H.; Thissell, J. G. Tetrahedron Lett. 1999, 40, 2677
13. For selected examples of radical addition to indoles and pyrroles, see
14. Baciocchi, E.; Muraglia, E. J. Org. Chem. 1993, 58, 7610
15. Byers, J. H.; DeWitt, A.; Nasveschuk, C. G.; Swigor, J. E. Tetrahedron Lett. 2004, 45, 6587
16. Guadarrama-Morales, O.; Méndez, F.; Miranda, L. D. Tetrahedron Lett. 2007, 48, 4515
17. Lindsay, K. B.; Ferrando, F.; Christensen, K. L.; Overgaard, J.; Roca, T.; Bennasar, M.; Skrydstrup, T. J. Org. Chem. 2007, 72, 4181
18. For a review on visible light photoredox catalysis and its applications in organic chemistry, see: Narayanam, J. M. R.; Stephenson, C. R. J. Chem. Soc. Rev. 2010, 39, DOI:10.1039/b913880n.
19. For recent examples, see
20. Nicewicz, D. A.; MacMillan, D. W. C. Science 2008, 322, 77
21. Ischay, M. A.; Anzovino, M. E.; Du, J.; Yoon, T. P. J. Am. Chem. Soc. 2008, 130, 12886
22. Koike, T.; Akita, M. Chem. Lett. 2009, 38, 166
23. Narayanam, J. M. R.; Tucker, J. W.; Stephenson, C. R. J. J. Am. Chem. Soc. 2009, 131, 8756
24. Nagib, D. A.; Scott, M. E.; MacMillan, D. W. C. J. Am. Chem. Soc. 2009, 131, 10875
25. Du, J.; Yoon, T. P. J. Am. Chem. Soc. 2009, 131, 14604
26. Condie, A. G.; González-Gómez, J. C.; Stephenson, C. R. J. J. Am. Chem. Soc. 2010, 132, 1464
27. Tucker, J. W.; Nguyen, J. D.; Narayanam, J. M. R.; Krabbe, S. W.; Stephenson, C. R. J. Chem. Commun. 2010, 46, DOI: 10.1039/c0cc00981d.
28. Tucker, J. W.; Narayanam, J. M. R.; Krabbe, S. W.; Stephenson, C. R. J. Org. Lett. 2010, 12, 368
29. The regioselectivity observed in this reaction (C2 vs. C3) is consistent with a radical process. For a recent example, see: Reyes-Gutiérrez, P. E.; Torres-Ochoa, R. O.; Martínez, R.; Miranda, L. D. Org. Biomol. Chem. 2009, 7, 1388.
30. 2.
31. The blue LEDs have a maximum emission at 435 nm (-±15 nm at half-maximum intensity). See the Supporting Information for further details.
32. Using a 14 W fluorescent light bulb, the reaction was complete in 5 days.
33. Functionalization of azaindoles is generally more challenging than indoles. For a review, see: Popowycz, F.; Routier, S.; Joseph, B.; Mérour, J.-Y. Tetrahedron 2007, 63, 1031
34. The excited-state Ru(II)* or radical-chain transfer to the benzylic bromide may be responsible for the benzylic oxidation; however, adventitious oxygen or triarylammonium radical cation cannot be ruled out at this time.