Noncryogenic preparation of functionalized arylboronic esters through a magnesium-iodine exchange with in situ quench

Organic Process Research and Development

Volumn 15, Issue 3, 2011, Pages 710-716

  Demory, Emilien ^a   Blandin, Véronique ^a   Einhorn, Jacques ^a   Chavant, Pierre Y ^a  

^a Centre National de la Recherche Scientifique   (France)

Author keywords

[No Author keywords available]

Indexed keywords

CHLORINE COMPOUNDS; ESTERS; GLYCOLS; IODINE; LITHIUM COMPOUNDS; MAGNESIUM; MAGNESIUM COMPOUNDS; REACTION INTERMEDIATES;

BORATE ESTERS; BORONIC ESTERS; CRUDE PRODUCTS; FUNCTIONALIZED; METAL-HALOGEN EXCHANGE; ORGANOMAGNESIUM; REACTION PARAMETERS; REACTIVE SPECIES;

PRASEODYMIUM COMPOUNDS;

EID: 79957512852     PISSN: 10836160     EISSN: 1520586X     Source Type: Journal    
DOI: 10.1021/op2000089     Document Type: Article

References (58)

1. Hall, D. G., Ed. Boronic Acids: Preparation and Applications in Organic Synthesis and Medicine; Wiley-VCH Verlag GmbH: Weinheim, 2005.
2. Borylation of arenes with pinacolborane or bis(pinacolato)diboron: Chen, H.; Schlecht, S.; Semple, T. C.; Hartwig, J. F. Science 2000, 287, 1995-1997
3. Cho, J.-Y.; Tse, M. K.; Holmes, D.; Maleczka, R. E., Jr.; Smith, M. R., III Science 2002, 295, 305-308 For a recent review, see: Mkhalid, I. A. I.; Barnard, J. H.; Marder, T. B.; Murphy, J. M.; Hartwig, J. F. Chem. Rev. 2010, 110, 890-931
4. Borylation of aryl halides with tetraoxydiboron reagents: Ishiyama, T.; Murata, M.; Miyaura, N. J. Org. Chem. 1995, 60, 7508-7510 For reviews, see: Ishiyama, T.; Chen, H. 4,4,4′,4′,5,5,5′,5′-Octamethyl-2, 2′-bi-1,3,2-dioxaborolane. In e-EROS Encyclopedia of Reagents for Organic Synthesis; 10.1002/047084289X.rn00188.pub2.
5. Merino, P.; Tejero, T. Angew. Chem., Int. Ed. 2010, 49, 7164-7165 See also: Billingsley, K. L.; Barder, T. E.; Buchwald, S. L. Angew. Chem., Int. Ed. 2007, 46, 5359-5363
6. Molander, G. A.; Trice, S. L. J.; Dreher, S. D. J. Am. Chem. Soc. 2010, 132, 17701-17703 Nevertheless, applicability on a large scale remains hampered by the access to the tetraoxydiboron reagents themselves: Ishiyama, T.; Murata, M.; Ahiko, T.-a.; Miyaura, N. Organic Syntheses; Wiley & Sons: New York, 2004; Collect. Vol. 10, pp 115 - 119.
7. Borylation of aryl halides with dialkoxyborane reagents: Pd catalysis: Murata, M.; Watanabe, S.; Masuda, Y. J. Org. Chem. 1997, 62, 6458-6459 Cu: Zhu, W.; Ma, D. Org. Lett. 2006, 8, 261-263 Ni: Morgan, A. B.; Jurs, J. L.; Tour, J. M. J. Appl. Polym. Sci. 2000, 76, 1257-1268
8. Rosen, B. M.; Huang, C.; Percec, V. Org. Lett. 2008, 10, 2597-2600 For bibliography, see: Moldoveanu, C.; Wilson, D. A.; Wilson, C. J.; Leowanawat, P.; Resmerita, A.-M.; Liu, C.; Rosen, B. M.; Percec, V. J. Org. Chem. 2010, 75, 5438-5452 and references therein.
9. Lam, K. C.; Marder, T. B.; Lin, Z. Organometallics 2010, 29, 1849-1857 and references therein. See also: Doux, M.; Mézailles, N.; Melaimi, M.; Ricard, L.; Le Floch, P. Chem. Commun. 2002, 1566-1567
10. Miller, W. D.; Fray, A. H.; Quatroche, J. T.; Sturgill, C. D. Org. Process Res. Dev. 2007, 11, 359-364
11. Recent examples. Organolithium reagents: Huang, S.; Petersen, T. B.; Lipshutz, B. H. J. Am. Chem. Soc. 2010, 132, 14021-14023
12. Clapham, K. M.; Batsanov, A. S.; Bryce, M. R.; Tarbit, B. Org. Biomol. Chem. 2009, 7, 2155-2161 Aryl Grignard reagent: Gerbino, D. C.; Mandolesi, S. D.; Schmalz, H.-G.; Podestá, J. C. Eur. J. Org. Chem. 2009, 3964-3972 For a 1.5-mol scale synthesis of an arylboronic acid via an organomagnesium species, see: Cladingboel, D. E. Org. Process Res. Dev. 2000, 4, 153-155
13. iPrMgCl•LiCl, see: Krasovskiy, A.; Knochel, P. Angew. Chem., Int. Ed. 2004, 43, 3333-3336
14. Boymond, L.; Rottländer, M.; Cahiez, G.; Knochel, P. Angew. Chem., Int. Ed. 1998, 37, 1701-1703
15. See for instance: Liu, C.-Y.; Gavryushin, A.; Knochel, P. Chem. Asian J. 2007, 2, 1020-1030
16. Hawkins, V. F.; Wilkinson, M. C.; Whiting, M. Org. Process Res. Dev. 2008, 12, 1265-1268
17. Reeves, J. T.; Sarvestani, M.; Song, J. J.; Tan, Z.; Nummy, L. J.; Lee, H.; Yee, N. K.; Senanayake, C. H. Org. Process Res. Dev. 2006, 10, 1258-1262
18. Tang, W.; Sarvestani, M.; Wei, X.; Nummy, L. J.; Patel, N.; Narayanan, B.; Byrne, D.; Lee, H.; Yee, N. K.; Senanayake, C. H. Org. Process Res. Dev. 2009, 13, 1426-1430
19. Lithium-halogen exchange: Li, W.; Nelson, D. P.; Jensen, M. S.; Hoerrner, R. S.; Cai, D.; Larsen, R. D.; Reider, P. J. J. Org. Chem. 2002, 67, 5394-5397
20. Stewart, G. W.; Brands, K. M. J.; Brewer, S. E.; Cowden, C. J.; Davies, A. J.; Edwards, J. S.; Gibson, A. W.; Hamilton, S. E.; Katz, J. D.; Keen, S. P.; Mullens, P. R.; Scott, J. P.; Wallace, D. J.; Wise, C. S. Org. Process Res. Dev. 2010, 14, 849-858 See also, for directed ortho metalation: Krizan, T. D.; Martin, J. C. J. Am. Chem. Soc. 1983, 105, 6155-6157
21. Caron, S.; Hawkins, J. M. J. Org. Chem. 1998, 63, 2054-2055
22. Kristensen, J.; Lysén, M.; Vedso, P.; Begtrup, M. Org. Lett. 2001, 3, 1435-1437
23. Alessi, M.; Larkin, A. L.; Ogilvie, K. A.; Green, L. A.; Lai, S.; Lopez, S.; Snieckus, V. J. Org. Chem. 2007, 72, 1588-1594
24. Meudt, A.; Nerdinger, S.; Erbes, M.; Vogt, W. Method for producing 2-formylfuran-4-boronic acid by the metalation of 4-halofurfural acetals in the presence of suitable boronic acid esters or anhydrides. WO/2006/122683, 2006. The magnesium-bromine exchange between 4-bromofurfural diethyl acetal and isopropylmagnesium bromide is performed in the presence of triisopropyl borate at low temperature (<-60 °C); after deprotection of the acetal, the corresponding arylboronic acid is recovered in 73% yield. Collibee, S. E.; Yu, J. Tetrahedron Lett. 2005, 46, 4453-4455 The "in situ quench" of an aryl Grignard reagent, prepared by magnesium-iodine exchange with phenylmagnesium chloride, with trimethyl borate at low temperature (-60 °C) gave poorer results (<10% yield in boronic acid) than a "sequential quenching" (85% yield).
25. Murata, M.; Oda, T.; Watanabe, S.; Masuda, Y. Synthesis 2007, 351-354
26. Murata, M.; Sambommatsu, T.; Oda, T.; Watanabe, S.; Masuda, Y. Heterocycles 2010, 80, 213-218
27. PraveenGanesh, N.; Chavant, P. Y. Eur. J. Org. Chem. 2008, 4690-4696
28. PraveenGanesh, N.; Demory, E.; Gamon, C.; Blandin, V.; Chavant, P. Y. Synlett 2010, 2403-2406
29. Chavant, P. Y.; PraveenGanesh, N. 4,4,6-Trimethyl-1,3,2-dioxaborinane. In e-EROS Encyclopaedia of Reagents for Organic Synthesis; John Wiley & Sons, Ltd.: New York; 2008; 10.1002/047084289X.rn01065.
30. See also: PraveenGanesh, N.; d'Hondt, S.; Chavant, P. Y. J. Org. Chem. 2007, 72, 4510-4514
31. PraveenGanesh, N.; de Candia, C.; Memboeuf, A.; Lendvay, G.; Gimbert, Y.; Chavant, P. Y. J. Organomet. Chem. 2010, 695, 2447-2454
32. For instance: hexylene glycol 99%, 500 g, Aldrich, 29.80; pinacol 98%, 500 g, Aldrich, 394.60.
33. Mehrotra, R. C.; Srivastava, G. J. Chem. Soc. 1962, 1032-1034
34. iPr was prepared from triisopropyl borate and hexylene glycol following the procedure for the pinacol derivative described in: Hoffmann, R. W.; Metternich, R.; Lanz, J. W. Liebigs Ann. Chem. 1987, 881 - 887.
35. iPrMgCl•LiCl (1.4 equiv, 1.3 M in THF, addition rate: 0.2 mL/min).
36. iPr, is present in the reaction mixture (as detected by GC analysis) but is easily eliminated under vacuum together with the solvents. Traces of polar boric acid derivatives are removed by filtration over silica gel.
37. iPr occurred instantaneously in the absence of the aryl iodide.
38. Delacroix, T.; Bérillon, L.; Cahiez, G.; Knochel, P. J. Org. Chem. 2000, 65, 8108-8110
39. Shi, L.; Chu, Y.; Knochel, P.; Mayr, H. Angew. Chem., Int. Ed. 2008, 47, 202-204
40. Shi, L.; Chu, Y.; Knochel, P.; Mayr, H. J. Org Chem. 2009, 74, 2760-2764
41. Shi, L.; Chu, Y.; Knochel, P.; Mayr, H. Org. Lett. 2009, 11, 3502-3505
42. Regarding the difference in reactivity between ArI and ArBr, see in particular ref 6b and references therein.
43. Sapountzis, I.; Knochel, P. Angew. Chem., Int. Ed. 2002, 41, 1610-1611
44. Sapountzis, I; Dube, H.; Lewis, R.; Gommermann, N.; Knochel, P. J. Org. Chem. 2005, 70, 2445-2454
45. For the preparation of the dimagnesium reagent from p -diiodobenzene, see: Krasovskiy, A.; Straub, F.; Knochel, P. Angew. Chem., Int. Ed. 2006, 45, 159-162
46. Formation of an aryne from o -halo magnesium species at room temperature, and even at -78 °C, has been hypothesized: Hart, H.; Harada, K.; Du, C.-J. F. J. Org. Chem. 1985, 50, 3104-3110
47. Ghosh, T.; Hart, H. J. Org. Chem 1988, 53, 3555-3558 Formation of 2-halo arylmagnesium species via magnesium-iodine exchange before addition of a trialkylborate was performed at low temperature: -78 °C: Baron, O.; Knochel, P. Angew. Chem., Int. Ed. 2005, 44, 3133-3135
48. Wegner, H. A.; Reisch, H.; Rauch, K.; Demeter, A.; Zachariasse, K. A.; de Meijere, A.; Scott, L. T. J. Org. Chem. 2006, 71, 9080-9087
49. Al-Zoubi, R. M.; Marion, O.; Hall, D. G. Angew. Chem., Int. Ed. 2008, 47, 2876-2879
50. Diemer, V.; Leroux, F. R.; Colobert, F.; Eur. J. Org. Chem 2011, 327-340 -30 °C: Huang, H.; Drueckhammer, D. G. Chem. Commun. 2006, 2995-2997 The 2-iodophenylmagnesium species is stable for 30 min at -20°C: Cvengros, J.; Stolz, D.; Togni, A. Synthesis 2009, 2818-2824
51. The Suzuki-Miyaura coupling was performed according to Buchwald's procedure: Barder, T. E.; Walker, S. D.; Martinelli, J. R.; Buchwald, S. L. J. Am. Chem. Soc. 2005, 127, 4685-4696, using 1.5 equiv of boronic ester. Interestingly, 0.3 equiv of unreacted arylboronic ester were recovered after chromatography, indicating that a lower excess could have been used
52. Fischer, F. C.; Havinga, E. Recl. Trav. Chim. Pays-Bas 1974, 93, 21-24 Bibliography, see: Campeau, F.-C.; Fagnou, K. Chem. Soc. Rev. 2007, 36, 1058-1068
53. Dick, G. R.; Knapp, D. M.; Gillis, A. P.; Burke, M. D. Org. Lett. 2010, 12, 2314-2317
54. See in particular refs 6a and 21c.
55. It is worth noting that anisyl halides are among the best substrates for all variants of Pd-catalyzed-borylation (which is fast and high-yielding with electron-rich substrates).
56. iPr 1 should be kept so that accidental excess of isopropylmagnesium halide will be trapped by 1.
57. iPr (1) is also commercially available (2-isopropoxy-4,4,6-trimethyl- 1,3,2-dioxaborinane, 99%, 5 mL, Aldrich, 20.20).
58. Watson, S. C.; Eastham, J. F. J. Organomet. Chem. 1967, 9, 165-168