Directed ortho borylation of functionalized Arenes catalyzed by a silica-supported compact phosphine-iridium system

Journal of the American Chemical Society

Volumn 131, Issue 14, 2009, Pages 5058-5059

  Kawamorita, Soichiro ^a,b   Ohmiya, Hirohisa ^a,b   Hara, Kenji ^a,c   Fukuoka, Atsushi ^a,c   Sawamura, Masaya ^a,b  

^a HOKKAIDO UNIVERSITY   (Japan)

^b Department of Chemistry ^*  (Japan)

^c Catalysis Research Cente

Author keywords

[No Author keywords available]

Indexed keywords

BORYLATION; C-H BOND; FUNCTIONALIZED; HIGH ACTIVITY; IN-SITU; MILD REACTION CONDITIONS;

AMIDES; BENZENE; ESTERS; IRIDIUM; PHOSPHORUS COMPOUNDS; SILICA;

AROMATIC COMPOUNDS;

BENZENE DERIVATIVE; IRIDIUM; PHOSPHINE DERIVATIVE; POLYCYCLIC AROMATIC HYDROCARBON DERIVATIVE; SILICON DIOXIDE;

ARTICLE; CATALYSIS; CATALYST; CHEMICAL BOND; CHEMICAL REACTION; SUBSTITUTION REACTION;

EID: 67849117187     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9008419     Document Type: Article

References (23)

1. (a) Jones, W. D. In Topics in Organometallic Chemistry 3: Activation of Unreactive Bonds and Organic Synthesis; Murai, S., Ed.; Springer: Berlin, 1999; pp 9-46.
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3. (c) Kakiuchi, F.; Chatani, N. Adv. Synth. Catal. 2003, 345, 1077-1101.
4. SMAP: silicon-constrained monodentate trialkylphosphine. See: (a) Ochida, A.; Hara, K.; Ito, H.; Sawamura, M. Org. Lett. 2003, 5, 2671-2674.
5. (b) Ochida, A.; Ito, S.; Miyahara, T.; Ito, H.; Sawamura, M. Chem. Lett. 2006, 35, 294-295.
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7. (a) Hamasaka, G.; Ochida, A.; Hara, K.; Sawamura, M. Angew. Chem., Int. Ed. 2007, 46, 5381-5383.
8. (b) Hamasaka, G.; Kawamorita, S.; Ochida, A.; Akiyama, R.; Hara, K.; Fukuoka, A.; Asakura, K.; Chun, W. J.; Ohmiya, H.; Sawamura, M. Organometallics 2008, 27, 6495-6506.
9. (c) Kawamorita, S.; Hamasaka, G.; Ohmiya, H.; Hara, K.; Fukuoka, A.; Sawamura, M. Org. Lett. 2008, 10, 4697-4700.
10. For a related study with a self-assembled monolayer of SMAP on a gold surface, see: Hara, K.; Akiyama, R.; Takakusagi, S.; Uosaki, K.; Yoshino, T.; Kagi, H.; Sawamura, M. Angew. Chem., Int. Ed. 2008, 47, 5627-5630.
11. For selected papers on the borylation of aromatic C-H bonds with bis(pinacolato)diboron, see: (a) Iverson, C. N.; Smith, M. R., III. J. Am. Chem. Soc. 1999, 121, 7696-7697.
12. (b) Cho, J.-Y.; Tse, M. K.; Holmes, D.; Maleczka, R. E., Jr.; Smith, M. R., III. Science 2002, 295, 305-308.
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14. (d) Ishiyama, T.; Takagi, J.; Hartwig, J. F.; Miyaura, N. Angew. Chem., Int. Ed. 2002, 41, 3056-3058.
15. (e) Boller, T. M.; Murphy, J. M.; Hapke, M.; Ishiyama, T.; Miyaura, N.; Hartwig, J. F. J. Am. Chem. Soc. 2005, 127, 14263-14278.
16. (a) Ortho borylation of methyl benzoates 1 with 2 (the directing group is CO2Me) in the presence of [Ir(OMe)(cod)]2 and P[3,5-(CF3)2C6H3]3 has been presented (e.g., 1f/2)5:1, 3 mol%Ir, 6 mol%P, octane, 80 ?C, 16 h, 98% GC yield of 3f). See: Isou, H.; Kikuchi, T.; Ishiyama, T.; Miyaura, N. Presented at the 88th Annual Meeting of the Chemical Society of Japan, Tokyo, March 26-30, 2008; 5H3- 15.
17. (b) Part of the work has been described in a review: Miyaura, N. Bull. Chem. Soc. Jpn. 2008, 81, 1535-1541.
18. For ortho borylation of arenes directed by a Me2HSi group, see: Boebel, T. A.; Hartwig, J. F. J. Am. Chem. Soc. 2008, 130, 7534-7535.
19. In Scheme 1, eq 1, and Tables 1 and 2, H-Bpin seems to have reacted with the arenes to some extent.
20. ICP-MS analysis of Ir leaching after the reaction (0.5 mol % catalyst loading, Table 1, entry 1, Celite-filtered) detected only 0.05% of the loaded Ir. The catalyst that was recovered by decantation showed decreased activities (∼80%) because of partial decomposition during the recycling process.
21. Even with 4-CF3-Ph-SMAP, Ph3P, (t-Bu)3P, Cy3P, or Me3P (1:1 or 1:2 Ir/P), the borylation of 1a proceeded at 70 ?C (20 h), but 3a was obtained in low yields or was contaminated with meta and para borylation products (see the Supporting Information).
22. For benzylic C-H borylation, see: Shimada, S.; Batsanov, A. S.; Howard, J. A. K.; Marder, T. B. Angew. Chem., Int. Ed. 2001, 40, 2168-2171.
23. The reactions of 1j, 1q, and 1r were carried out with the dtbpy- Ir(OMe)(cod) system under the corresponding conditions shown in Tables 1 and 2. The reaction of 1q provided 3q exclusively, but the reactions of 1j and 1r did not proceed at all.