Arylmagnesiation of alkynes catalyzed cooperatively by iron and copper complexes

Journal of the American Chemical Society

Volumn 127, Issue 49, 2005, Pages 17164-17165

  Shirakawa, Eiji ^a   Yamagami, Takafumi ^a   Kimura, Takahiro ^a   Yamaguchi, Shigeru ^a   Hayashi, Tamio ^a  

^a KYOTO UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ALKYNE; COPPER COMPLEX; IRON COMPLEX; MAGNESIUM;

ARTICLE; ARYLATION; CATALYSIS; CHEMICAL MODIFICATION; HYDROLYSIS; STEREOCHEMISTRY;

EID: 29044439620     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0542136     Document Type: Article

References (32)

1. Knochel, P. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Semmelhack, M. F., Eds.; Pergamon Press: New York, 1991; Vol. 4, Chapter 4.4; pp 865-911.
2. For a recent review on carbometalation of heteroatom-containing alkynes and alkenes, see: Fallis, A. G.; Forgione, P. Tetrahedron 2001, 57, 5899-5913.
3. Unfunctionalized alkynes used for the arylmetalation are all aryl-substituted acetylenes. For examples, see: (a) Eisch, J. J.; Kaska, W. C. J. Am. Chem. Soc. 1966, 88, 2976-2983.
4. (b) Eisch, J. J.; Amtmann, R.; Foxton, M. W. J. Organomet. Chem. 1969, 16, P55-59.
5. (c) Eisch, J. J.; Amtmann, R. J. Org. Chem. 1972, 37, 3410-3415.
6. (d) Duboudin, J. G.; Jousseaume, B. J. Organomet. Chem. 1978, 162, 209-222.
7. (e) Stüdemann, T.; Knochel, P. Angew. Chem., Int. Ed. Engl. 1997, 36, 93-95.
8. (f) Yorimitsu, H.; Tang, J.; Okada, K.; Shinokubo, H.; Oshima, K. Chem. Lett. 1998, 11-12.
9. In the study on the iron-catalyzed alkyllithiation of heteroatom-containing alkynes, the corresponding alkyl- and allylmagnesiations have been conducted for comparison: Hojo, M.; Murakami, Y.; Aihara, H.; Sakuragi, R.; Baba, Y.; Hosomi, A. Angew. Chem., Int. Ed. 2001, 40, 621-623.
10. The iron-catalyzed carbometalation of alkynes is likely involved in the regioselective reaction of propargyl epoxides with Grignard reagents. (a) Fürstner, A.; Méndez, M. Angew. Chem., Int. Ed. 2003, 42, 5355-5357.
11. (b) Lepage, O.; Kattnig, E.; Fürstner, A. J. Am. Chem. Soc. 2004, 126, 15970-15971.
12. For examples of the iron-catalyzed carbometalations of alkynes using organometallic compounds other than Grignard reagents, see: (a) Caporusso, A. M.; Lardicci, L.; Giacomelli, G. Tetrahedron Lett. 1977, 18, 4351-4354.
13. (b) Caporusso, A. M.; Giacomelli, G.; Lardicci, L. J. Chem. Soc., Perkin Trans. 1 1979, 3139-3145.
14. The iron-catalyzed carbometalation of an alkene, a cyclopropenone acetal, using Grignard reagents including arylmagnesium bromide has been reported. Nakamura, M.; Hirai, A.; Nakamura, E. J. Am. Chem. Soc. 2000, 122, 978-979.
15. For recent reviews on the iron-catalyzed reactions including carbometalation of carbon-carbon unsaturated bonds, see: (a) Bolm, C.; Legros, J.; Le Paih, J.; Zani, L. Chem. Rev. 2004, 104, 6217-6254.
16. (b) Fürstner, A.; Martin, R. Chem. Lett. 2005, 34, 624-629.
17. For examples of the copper-catalyzed carbomagnesiation. see: (a) Duboudin, J. G.; Jousseaume, B. J. Organomet. Chem. 1979, 168, 1-11.
18. (b) Xie, M.; Huang, X. Synlett 2003, 477-480.
19. One of the earliest and the most effective examples of this type of the cooperative catalysis is the Sonogashira coupling, where palladium and copper catalysts activate aryl halides and terminal alkynes, respectively. (a) Sonogashira, K.; Tohda, Y.; Hagihara, N. Tetrahedron Lett. 1975, 16, 4467-4470.
20. For an account, see: (b) Sonogashira, K. J. Organomet. Chem. 2002, 653, 46-49.
21. The cooperative catalysis has recently been reviewed with an appropriate classification: (c) Lee, J. M.; Na, Y.; Han, H.; Chang, S. Chem. Soc. Rev. 2004, 33, 302-312.
22. See also the following reviews: (d) van den Beuken, E. K.; Feringa, B. L. Tetrahedron 1998, 54, 12985-13011.
23. (e) Chen, E. Y.-X.; Marks, T. J. Chem. Rev. 2000, 100, 1391-1434.
24. 1H NMR.
25. 3 can be reduced to 10 mol % (Fe: 3 mol %; Cu: 6 mol %) without significant loss of the yield (61%, E:Z = 91:9). For the experimental conditions, see Supporting Information.
26. 3, and dppp) and with nitrogen ligands (pyridine and substituted pyridines).
27. High regioselectivities for aryl(alkyl)alkynes were also reported in the arylmetalations. See refs 3a, d-f.
28. A mixture of two diastereomeric isomers, both of which have (Z)-configuration, due to the central chirality at the α-carbon of the allylic alcohol and the axial chirality based on the restricted rotation about the naphthyl-alkenyl bond.
29. 3 with alkylmagnesium bromides. Kauffmann, T.; Laarmann, B.; Menges, D.; Voss, K.-U.; Wingbermünster, D. Tetrahedron Lett. 1990, 31, 507-510.
30. Rahman, M. T.; Hoque, A. K. M. M.; Siddique, I.; Chowdhury, D. A. N.; Nahar, S. K.; Saha, S. L. J. Organomet. Chem. 1980, 188, 293-300.
31. Arylcuprates generated in situ from CuCN-2LiCl and arylmagnesium iodides are used effectively in the iron-catalyzed coupling with aryl iodides. Sapountzis, I.; Lin, W.; Kofink, C. C.; Despotopoulou, C.; Knochel, P. Angew. Chem., Int. Ed. 2005, 44, 1654-1657.
32. Transmetalation between alkenyl(aryl)cuprates and arylmagnesium bromides should be involved in the copper-catalyzed arylmagnesiation of propargyl alcohols or sulfonylacetylenes. See ref 7.