Palladium-catalyzed fluorination of carbon-hydrogen bonds

Journal of the American Chemical Society

Volumn 128, Issue 22, 2006, Pages 7134-7135

  Hull, Kami L ^a   Anani, Waseem Q ^a   Sanford, Melanie S ^a  

^a UNIVERSITY OF MICHIGAN   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

8 FLUOROMETHYLQUINOLINE; CARBON; FLUORINE; HYDROGEN; ORGANOMETALLIC COMPOUND; PALLADIUM; QUINOLINE DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CATALYSIS; COMPLEX FORMATION; FLUORINATION; HYDROGEN BOND; HYDROPHOBICITY; MOLECULAR INTERACTION; OXIDATION REDUCTION REACTION;

CARBON; CATALYSIS; HYDROCARBONS, FLUORINATED; HYDROGEN BONDING; MOLECULAR STRUCTURE; PALLADIUM; QUINOLINES;

EID: 33744928374     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja061943k     Document Type: Article

References (22)

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2. For metal-catalyzed α-fluorination of carbonyl compounds, see: (a) Ibrahim, H.; Togni, A. Chem. Commun. 2004, 1147-1155.
3. (b) Hamashima, Y.; Suzuki, T.; Takano, H.; Shimura, Y.; Sodeoka, M. J. Am. Chem. Soc. 2005, 127, 10164-10165 and references therein.
4. Grushin, V. V. Chem.-Eur. J. 2002, 8, 1006-1014 and references therein.
5. Handbook of Organopalladium Chemistry for Organic Synthesis; Negishi, E. I., Ed.; Wiley-Interscience: New York, 2002.
6. II, where C = acyl, has been reported. Fraser, S. L.; Antipin, V. N.; Khroustalyov, V. N.; Grushin, V. V. J. Am. Chem. Soc. 1997, 119, 4769-4770.
7. In contrast, the microscopic reverse of this process-C-F bond oxidative addition-is well-known. For reviews, see: (a) Burdeniuc, J.; Jedlicka, B.; Crabtree, R. H. Chem. Ber. Recl. 1997, 130, 145-154.
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10. 0, see: (d) Jasim, N. A.; Perutz, R. N.; Whitwood, A. C.; Braun, T.; Izundu, J.; Neumann, B.; Rothfeld, S.; Stammler, H. G. Organomelallics 2004, 23, 6140-6149.
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16. II has strict electronic requirements: Widenhoefer, R. A.; Buchwald, S. L. J. Am. Chem. Soc. 1998, 120, 6504-6511.
17. eq: Roy, A. H.; Hartwig, J. F. Organometallics 2004, 23, 1533-1541.
18. For C-H activation/functionalization reactions accelerated by microwave heating, see: Lewis, J. C.; Wu, J. Y.; Bergman, R. G.; Ellman, J. A. Angew. Chem., Int. Ed. 2005, 45, 1589-1591.
19. 2 catalyst, and this product could be generated by either Pd-catalyzed or non-Pd-mediated reactions. See the Supporting Information for a full discussion of these possibilities.
20. For a review that discusses Pd-catalyzed oxidative coupling reactions, see: Stahl, S. S. Angew. Chem., Int. Ed. 2004, 43, 3400-3420.
21. 3 group was favored (with a product ratio of 29:1). Ongoing work seeks to more fully elucidate the mechanism of this unusual arylation reaction.
22. Additionally, 4a also does not react with aromatic solvents in the presence of oxidants 2 or 3 to afford arylated side products analogous to 1b. These data are consistent with the hypothesis that 1b is formed by an electrophilic mechanism, possibly involving a transient benzylic cation.