Organotrifluoroborates: Potent Boronic Acid Surrogates

In the vast array of catalytic carbon-carbon bond forming reactions, the Suzuki-Miyaura protocol has proven to be a particularly attractive method.  The organoborane nucleophiles (boronic acids, boronate esters, and potassium organotrifluoroborates) readily undergo cross-coupling under mild conditions and in the presence of ordinarily sensitive functional groups (e.g. OH, CO₂H, CN, CHO, etc).  However, both boronic acids and boronate esters suffer from limitations.  Boronic acids are difficult to purify and can have uncertain stoichiometry due to trimerization to the corresponding boroxine.  Boronate esters lack atom economy and are more expensive due to the added cost of pinacol or catechol (Figure 1).

Alternatively, potassium organotrifluoroborates:  have known stoichiometry, have a low molecular weight, are insensitive to air and moisture, and are tractable, crystalline solids which are easily stored (Figure 2).¹

Potassium alkyl-, alkenyl-, aryl-, and heteroaryltrifluoroborates participate in Suzuki-Miyaura cross-coupling reactions yielding versatile synthetic intermediates including:  1,3-dienes, styrenes, sterically hindered biaryls, and highly functionalized heterocyclics (Figure 3).²

In addition to Suzuki-Miyaura coupling, potassium organotrifluoroborates participate in a variety of other useful reactions including:  1,2- and 1,4-addition, C—O and C—N bond formation, and halogenation, and allylation (Figure 4).³

   Product Information

Product #  Product Name Product Structure Add to Cart 637890 Potassium methyltrifluoroborate 659274 Potassium allyltrifluoroborate, 95% 660094 Potassium butyltrifluoroborate, 95% 563056 Potassium benzyltrifluoroborate, 95% 563099 Potassium phenethyltrifluoroborate, 95% 655228 Potassium vinyltrifluoroborate, 95% 637882 Potassium trans-1-decenyltrifluoroborate, 95% 576158 Potassium trans-styryltrifluoroborate 563951 Potassium phenyltrifluoroborate, 95% 571547 Potassium 4-bromophenyltrifluoroborate 571555 Potassium p-tolyltrifluoroborate 571563 Potassium 3,5-bis(trifluoromethyl)-phenyltrifluoroborate 571598 Potassium 3-nitrophenyltrifluoroborate 576093 Potassium 4-formylphenyltrifluoroborate 576107 Potassium 2-bromophenyltrifluoroborate, 96% 576115 Potassium 3-methoxyphenyltrifluoroborate, 96% 576123 Potassium o-tolyltrifluoroborate 576131 Potassium 4-(trifluoromethyl)-phenyltrifluoroborate, 96% 579068 Potassium 4-methoxyphenyltrifluoroborate, 95% 592846 Potassium 4-fluorophenyltrifluoroborate, 95% 592943 Potassium 2,6-dimethylphenyltrifluoroborate, 95% 597929 Potassium 2,6-difluorophenyltrifluoroborate 654728 Potassium 4-tert-butylphenyltrifluoroborate, 95% 654930 Potassium 2-methoxyphenyltrifluoroborate, 95% 656992 Potassium 2,4-difluorophenyltrifluoroborate, 95% 657018 Potassium 2-naphthalenetrifluoroborate 657050 Potassium 4-acetylphenyltrifluoroborate, 97% 657069 Potassium 4-carboxyphenyltrifluoroborate, 97% 657077 Potassium 4-chlorophenyltrifluoroborate, 95% 657085 Potassium 2,6-dimethoxyphenyltrifluoroborate, 95% 657093 Potassium 3-formylphenyltrifluoroborate, 95% 657115 Potassium 4-(methylthio)-phenyltrifluoroborate, 95% 659746 Potassium 3-hydroxyphenyltrifluoroborate, 96% 659762 Potassium 4-(hydroxymethyl)-phenyltrifluoroborate 659770 Potassium 3-fluorophenyltrifluoroborate, 96% 659789 Potassium 3-carboxyphenyltrifluoroborate, 97% 659754 Potassium 3,4-(methylenedioxy)-phenyltrifluoroborate 571571 Potassium 3-thiophenetrifluoroborate 654949 Potassium 5-methyl-2-thiophenetrifluoroborate, 95%

Cheminar^TM 1.2 Potassium Organotrifluoroborates: High-Performance Boronic             Acid/Ester Surrogates

Cheminar^TM 1.2 Potassium Organotrifluoroborates: High-Performance Boronic             Acid/Ester Surrogates

References:

1. For recent reviews, see:  (a) Molander, G. A.; Figueroa, R. Aldrichimica Acta 2005, 38, 49-56; (b) Genêt, J.-P.; Darses, S. Eur. J. Org. Chem. 2003, 4313-4327.

2. (a) Molander, G. A.; Ribagorda, M. J. Am. Chem. Soc. 2003, 125, 11148-11149; (b) Molander, G. A.; Ito, T. Org. Lett. 2001, 3, 393-396; (c) Molander, G. A.; Yun, C-S.; Ribagorda, M.; Biolatto, B. J. Org. Chem. 2003, 68, 5534-5539; (d) Fang, G.-H.; Yan, Z.-J.; Deng, M-H. Org. Lett. 2004, 6, 357-360; (e) Charette, A. B.; Mathieu, S.; Fournier, J.-F. Synlett 2005, 11, 1779-1782; (f) Molander, G. A.; Felix, L. A. J. Org. Chem. 2005, 70, 3950-3956; (g) Molander, G. A.; Rivero, M. R. Org. Lett. 2002, 4, 107-109; (h) Molander, G. A.; Bernardi, C. R. J. Org. Chem. 2002, 67, 8424-8429; (i) Molander, G. A.; Katona, B. W.; Machrouhi, F. J. Org. Chem. 2002, 67, 8416-8423; (j) Molander, G. A.; Biolatto, B. Org. Lett. 2002, 4, 1867-1870; (k) Molander, G. A.; Biolatto, B. J. Org. Chem. 2003, 68, 4302-4314; (l) Barder, T. E.; Buchwald, S. L. Org. Lett. 2004, 6, 2649-2652; (m) Kabalka, G. W.; Al-Masum, M. Tetrahedron Lett. 2005, 46, 6329-6331.

3. (a) Batey, R. A.; Thadani, A. N.; Smil, D. V. Org. Lett. 1999, 1, 1683-1686; (b) Bolshan, Y.; Batey, R. A. Org. Lett. 2005, 7, 1481-1484; (c) Pucheault, M.; Darses, S.; Genêt, J.-P. Tetrahedron Lett. 2002, 43, 6155-6157; (d) Pucheault, M.; Darses, S.; Genêt, J.-P. Eur. J. Org. Chem. 2002, 3552-3557; (e) Duursma, A.; Boiteau, J.-G.; Lefort, L.; Boogers, J. A. F.; de Vries, A. H. M.; de Vries, J. G.; Minnaard, A. J.; Feringa, B. L. J. Org. Chem. 2004, 69, 8045-8052; (f) Darses, S.; Genêt, J.-P. Eur. J. Org. Chem. 2004, 69-73; (g) Quach, T. D.; Batey, R. A. Org. Lett. 2003, 5, 1381-1384; (h) Quach, T. D.; Batey, R. A. Org. Lett. 2003, 5, 4397-4400; (i) Batey, R. A.; Thadani, A. N.; Smil, D. V.; Lough, A. J. Synthesis 2000, 7, 990-998; (j) Batey, R. A.; Thadani, A. N.; Smil, D. V. Tetrahedron Lett. 1999, 40, 4289-4292; (k) Thadani, A. N.; Batey, R. A. Org. Lett. 2002, 4, 3827-3830; (l) Solin, N.; Wallner, O. A.; Szabó, K. J. Org. Lett. 2005, 7, 689-691; (m) Kabalka, G. W.; Venkataiah, B.; Dong, G. Org. Lett. 2003, 5, 3803-3805; (n) Kabalka, G. W.; Mereddy, A. R. Organometallics 2004, 23, 4519-4521; (o) Kabalka, G. W.; Mereddy, A. R. Tetrahedron Lett. 2004, 45, 343-345; (p) Kabalka, G. W.; Mereddy, A. R. Tetrahedron Lett. 2004, 45, 1417-1419.