Improved method for the conversion of pinacolboronic esters into trifluoroborate salts: facile synthesis of chiral secondary and tertiary trifluoroborates

Tetrahedron

Volumn 65, Issue 48, 2009, Pages 9956-9960

  Bagutski, Viktor ^a   Ros, Abel ^a   Aggarwal, Varinder K ^a  

^a UNIVERSITY OF BRISTOL   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

BORIC ACID; ESTER DERIVATIVE; SODIUM CHLORIDE;

ARTICLE; CHIRALITY; ENANTIOMER; METHODOLOGY; PINACOL REARRANGEMENT; PRIORITY JOURNAL; QUANTITATIVE ANALYSIS; REACTION ANALYSIS; SYNTHESIS;

EID: 70350442360     PISSN: 00404020     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tet.2009.10.002     Document Type: Article

References (44)

1. For reviews on preparation and use of trifluoroborates, see:
2. Darses S., and Genêt J.-P. Eur. J. Org. Chem. (2003) 4313-4327
3. Molander G.A., and Figueroa R. Aldrichimica Acta 38 (2005) 49-56
4. Molander G.A., and Ellis N. Acc. Chem. Res. 40 (2007) 275-286
5. Darses S., and Genêt J.-P. Chem. Rev. 108 (2008) 288-325
6. For seminal contributions to the area see:. Darses S., Genêt J.-P., Brayer J.-L., and Demoute J.-P. Tetrahedron Lett. 38 (1997) 4393-4396
7. Darses S., Michaud G., and Genêt J.-P. Tetrahedron Lett. 39 (1998) 5045-5048
8. Molander G.A., and Ito T. Org. Lett. 3 (2001) 393-396
9. Molander G.A., Yun C.-S., Rigaborda M., and Biolatto B. J. Org. Chem. 68 (2003) 5534-5539
10. Dreher S.D., Dormer P.G., Sandrock D.L., and Molander G.A. J. Am. Chem. Soc. 130 (2008) 9257-9259
11. Van den Hoogenband A., Lange J.H.M., Terpstra J.W., Koch M., Visser G.M., Visser M., Korstanje T.J., and Jastrzebski J.T.B.H. Tetrahedron Lett. 49 (2008) 4122-4124
12. For a recent breakthrough in the Suzuki-Miyaura coupling of secondary benzylic boronic esters see:. Imao D., Glasspoole B.W., Laberge V.S., and Crudden C.M. J. Am. Chem. Soc. 131 (2009) 5024-5025
13. Batey R.A., Thadani A.N., and Smil D.V. Org. Lett. 1 (1999) 1683-1686
14. Pucheault M., Darses S., and Genêt J.-P. Tetrahedron Lett. 43 (2002) 6155-6157
15. Pucheault M., Darses S., and Genêt J.-P. Eur. J. Org. Chem. (2002) 3552-3557
16. Pucheault M., Darses S., and Genêt J.-P. Chem. Commun. (2005) 4714-4716
17. Lalic G., and Corey E.J. Org. Lett. 9 (2007) 4921-4923
18. Lalic G., and Corey E.J. Tetrahedron Lett. 49 (2008) 4894-4896 for a recent example of the coupling of secondary and tertiary benzylic trifluoroborates with aldehydes see:
19. Ros A., and Aggarwal V.K. Angew. Chem., Int. Ed. (2009) 10.1002/anie.200901900
20. Lee S., and MacMillan D.W.C. J. Am. Chem. Soc. 129 (2007) 15438-15439
21. Kim H., and MacMillan D.W.C. J. Am. Chem. Soc. 130 (2008) 398-399
22. Matteson D.S., and Kim G.Y. Org. Lett. 4 (2002) 2153-2155
23. Epoxidation of double bond:
24. Molander G.A., and Rigaborda M. J. Am. Chem. Soc. 125 (2003) 11148-11149 Oxidation of hydroxymethyl group:
25. Molander G.A., and Petrillo D.E. J. Am. Chem. Soc. 128 (2006) 9634-9635 'Click-chemistry':
26. Molander G.A., and Ham J. Org. Lett. 8 (2006) 2767-2770 Lithiations:
27. Molander G.A., and Ellis N. J. Org. Chem. 71 (2006) 7491-7493 Nucleophilic substitutions:
28. Molander G.A., and Ham J. Org. Lett. 8 (2006) 2031-2034
29. Molander G.A., Febo-Ayala W., and Ortega-Guerra M. J. Org. Chem. 73 (2008) 6000-6002 Ozonolysis of double bond:
30. Molander G.A., and Cooper D.J. J. Org. Chem. 72 (2007) 3558-3560 HWE reactions:
31. Molander G.A., and Figueroa R. J. Org. Chem. 71 (2006) 6135-6140
32. Vedejs E., Chapman R.W., Fields S.C., Lin S., and Schrimpf M.R. J. Org. Chem. 60 (1995) 3020-3027
33. Vedejs E., Fields S.C., Hayashi R., Hitchcock S.R., Powell D.R., and Schrimpf M.R. J. Am. Chem. Soc. 121 (1999) 2460-2470
34. Darses S., Michaud G., and Genêt J.-P. Eur. J. Org. Chem. (1999) 1875-1883
35. According to SciFinder, 135 organic trifluoroborates are currently commercially available.
36. Stymiest J.L., Dutheuil G., Mahmood A., and Aggarwal V.K. Angew. Chem., Int. Ed. 46 (2007) 7491-7494
37. Stymiest J.L., Bagutski V., French R.M., and Aggarwal V.K. Nature 456 (2008) 778-782
38. Harwood L.M. Aldrichimica Acta 18 (1985) 25
39. Pedersen D.S., and Rosenbohm C. Synthesis (2001) 2431-2434
40. Yuen A.K.L., and Hutton C.A. Tetrahedron Lett. 46 (2005) 7899-7903
41. Murphy J.M., Tzschucke C.C., and Hartwig J.F. Org. Lett. 9 (2007) 757-760
42. 11B NMR monitoring of reaction of trifluoroborate 3k with an excess of neat pinacol. Thus, at 50 °C, 12% of 3k was converted into 2k after 20 h, whereas, after 12 h at 80 °C, the conversion reached 40%. It is also worthy to note that 3k could eventually be recrystallised (10% acetone in hexane, ∼0.1 g/mL) after three evaporation-dissolution cycles had been applied, though the yield decreased significantly.
43. See Supplementary data.
44. Chen A., Ren L., and Crudden C.M. J. Org. Chem. 64 (1999) 9704-9710