A New, Highly Selective Rh(III) Catalytic System for Carboxylation of Arenes via C-H Activation under Mild Conditions

Advanced Synthesis and Catalysis

Volumn 343, Issue 2, 2001, Pages 161-165

  Grushin, Vladimir V ^a   Marshall, William J ^a   Thorn, David L ^a  

^a DUPONT COMPANY   (United States)

Author keywords

Arenes; C H activation; Carboxylic acids; Homogeneous catalysis; Oxidative carbonylation; Rhodium

Indexed keywords

EID: 0001538186     PISSN: 16154150     EISSN: None     Source Type: Journal    
DOI: 10.1002/1615-4169(20010226)343:2<161::AID-ADSC161>3.0.CO;2-7     Document Type: Review

References (43)

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19. 2 = 97:3) but requires high pressures of 130-270 atm at 150°C.
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21. (a) L. Yu. Ukhin, Yu. A. Shvetsov, Izv. Akad. Nauk SSSR, Ser. Khim.. 1972, 1653; see also: F. J. Lahoz, A. Martin, M. A. Esteruelas, E. Sola, J. L. Serrano, L. A. Oro, Organometallics, 1991, 10, 1794;
22. -3. Crystallographic data for the structure reported in this paper have been deposited with the Cambridge Crystallographic Data Center as supplementary publication no. CCDC 145577. Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK [fax: (+44) 1223-336-033; e-mail: deposit@ccdc.cam.ac.uk].
23. 2 was observed at 124.8 ppm;
24. 2 in TFAH affords highly soluble, catalytically active Cl-free Rh(III)-TFA species;
25. (c) N. F. Gol'dshleger, A. P. Moravskii, Yu. M. Shul'ga, Izv. Akad. Nauk SSSR, Ser. Khim. 1991, 258; Yu. M. Shul'ga, N. F. Gol'dshleger, V. I. Rubtsov, V. I. Sokol, Izv. Akad. Nauk SSSR, Ser. Khim. 1992, 1549; N. F. Gol'dshleger, Yu. M. Shul'ga, O. S. Roshchupkina, Russ. J. Gen. Chem. 1998, 68, 339.
26. (c) N. F. Gol'dshleger, A. P. Moravskii, Yu. M. Shul'ga, Izv. Akad. Nauk SSSR, Ser. Khim. 1991, 258; Yu. M. Shul'ga, N. F. Gol'dshleger, V. I. Rubtsov, V. I. Sokol, Izv. Akad. Nauk SSSR, Ser. Khim. 1992, 1549; N. F. Gol'dshleger, Yu. M. Shul'ga, O. S. Roshchupkina, Russ. J. Gen. Chem. 1998, 68, 339.
27. (c) N. F. Gol'dshleger, A. P. Moravskii, Yu. M. Shul'ga, Izv. Akad. Nauk SSSR, Ser. Khim. 1991, 258; Yu. M. Shul'ga, N. F. Gol'dshleger, V. I. Rubtsov, V. I. Sokol, Izv. Akad. Nauk SSSR, Ser. Khim. 1992, 1549; N. F. Gol'dshleger, Yu. M. Shul'ga, O. S. Roshchupkina, Russ. J. Gen. Chem. 1998, 68, 339.
28. Both main group and transition metal trifluoroacetates possess much higher electrophilicity than corresponding acetates. See, for example: N. F. Gol'dshleger, A. P. Moravskii, Russ. Chem. Rev. 1994, 63, 125; D. L. Thorn, V. V. Grushin, W. J. Marshall, to be published.
29. Both main group and transition metal trifluoroacetates possess much higher electrophilicity than corresponding acetates. See, for example: N. F. Gol'dshleger, A. P. Moravskii, Russ. Chem. Rev. 1994, 63, 125; D. L. Thorn, V. V. Grushin, W. J. Marshall, to be published.
30. [13c]
31. (b) For reviews, see: A. Sen, Top. Organomet. Chem.. 1999, 3, 81; Acc. Chem. Res., 1998, 31, 550;
32. (b) For reviews, see: A. Sen, Top. Organomet. Chem.. 1999, 3, 81; Acc. Chem. Res., 1998, 31, 550;
33. (c) Very recently, Fujiwara and co-workers reported the Pd-or Pt-catalyzed hydroarylation of alkynes in the presence of TFAH: C. Jia, D. Piao, J. Oyamada, W. Lu, T. Kitamura, Y. Fujiwara, Science. 2000, 287, 1992; C. Jia, W. Lu, J. Oyamada, T. Kitamura, K. Matsuda, M. Irie, Y. Fujiwara, J. Am. Chem. Soc., 2000, 122, 7252.
34. (c) Very recently, Fujiwara and co-workers reported the Pd-or Pt-catalyzed hydroarylation of alkynes in the presence of TFAH: C. Jia, D. Piao, J. Oyamada, W. Lu, T. Kitamura, Y. Fujiwara, Science. 2000, 287, 1992; C. Jia, W. Lu, J. Oyamada, T. Kitamura, K. Matsuda, M. Irie, Y. Fujiwara, J. Am. Chem. Soc., 2000, 122, 7252.
35. 8/TFAH and produce a sufficiently reactive Rh(III) electrophile.
36. 1 = 30 sec) of the product.
37. J. March, Advanced Organic Chemistry, 3rd Edn., Wiley Interscience, New York, 1985, pp 447-453.
38. 6 species is expected to be octahedral or pentacoordinate and hence possess considerable steric bulk. This would account for the lack of reactivity at the orthopositions of toluene.
39. 1H NMR analysis of the product.
40. The difference in the para-selectivity of the carbonylation (>90%) and H/D exchange (ca. 70%) may be due to slightly different rates of CO insertion into the m-Tol-Rh and p-Tol-Rh bonds.
41. 8.
42. n.
43. +.