582
D. Haddenham et al. / Tetrahedron 67 (2011) 576e583
1
43.1; 11B NMR (160 MHz, MeOH)
for C 165.11054, found 165.10814.
d
þ29.1; EM (ESI): m/z (Mþ) calcd
MeOD)
found 176.08774.
d
þ28.3; EM (ESI): m/z (Mþ) calcd for C
9
H11BNO
2
176.09440,
9 2
H14BO
21
1
21
1
4
.4.3. 2-Tolylboronic acid (5c) (7c) (9c) . Off-white solid, H NMR
4.4.14. Naphthalen-2-ylboronic acid (9i) . Off-white solid, H NMR
(
500 MHz, CDCl
3
)
d
2.86 (s, 3H), 7.31 (d, 1H, J¼8.0 Hz), 7.35 (t, 1H,
(500 MHz, MeOH-d
4
)
d
7.48 (m, 2H), 7.76e7.89 (m, 4H), 8.24 (m,
1H); C NMR (125 MHz, MeOH-d 126.8,127.7,128.7,129.6,131.4,
þ29.3; EM (ESI): m/z (Mþ)
223.09631, found 223.09008.
13
13
J¼7.5 Hz), 7.49 (t, 1H, J¼7.5 Hz), 8.26 (d, 1H, J¼7.0 Hz); C NMR
4
) d
4
) d
11
11
(
(
C
125 MHz, CDCl
160 MHz, MeOH)
13BNaO 187.10383, found 187.09008.
3
)
d
23.3, 125.4, 130.8, 132.4, 137.5, 146.5; B NMR
135.7; B NMR (160 MHz, MeOH-d
calcd for C12 13BNaO
d
þ28.5; EM (ESI): m/z (Mþ) calcd for
H
2
9
H
2
4
.4.15. 4,4,5,5-tetramethyl-2-p-tolyl-1,3,2-dioxaborolane
2
1
1
23
1
4
.4.4. Phenylboronic acid (5d) (7d) (9e) . Off-white solid, H NMR
500 MHz, CDCl
7.54 (t, 2H, J¼7.5 Hz), 7.62 (t, 1H, J¼7.5 Hz), 8.27
d, 2H, J¼7.0 Hz); C NMR (125 MHz, CDCl
1
3
(10a) . Yellow Oil, H NMR (500 MHz, CDCl ) d 1.38 (s, 8H), 2.40 (s,
13
(
(
3
)
d
3H), 7.23 (d, 2H, J¼8.0 Hz), 7.77 (d, 2H, J¼8 Hz); C NMR (125 MHz,
1
3
11
3
)
d
128.1, 132.9, 135.8;
þ28.5; EM (ESI): m/z (Mþ) calcd for
151.08092, found 151.09249.
CDCl
CDCl
3
)
)
d
21.8, 24.9, 83.7, 128.7, 135.0, 141.5; B NMR (160 MHz,
þ31.3.
1
B NMR (160 MHz, MeOH)
d
3
d
C
8
H12BO
2
4
.4.16. 2-(4-methylphenyl)-5,5-dimethyl-1,3,2-dioxaborinane
21
6b,7a,20a
1
4
.4.5. 4-Fluorophenylboronic acid (5e) (7e) (9g) . Off-white solid,
(10b)
3
. Yellow Oil, H NMR (500 MHz, CDCl ) d 1.06 (s, 6H),
1
H NMR (500 MHz, CDCl
3
)
d
7.21 (t, 2H, J¼9.0 Hz), 8.24 (t, 2H,
2.41 (s, 3H), 3.80 (s, 4H), 7.23 (d, J¼8.0 Hz), 7.77 (d, 2H, J¼6.0 Hz);
13
13
J¼8.5 Hz); C NMR (125 MHz, MeOD) 112.2 (d, J ¼20 Hz),134.0 (d,
d
F
C NMR (125 MHz, CDCl
3
)
d
21.7, 22.0, 31.9, 72.4, 128.5, 134.1, 140.8;
þ27.1; EM (ESI): m/z (Mþ) calcd for
1
1
11
J
F
¼8 Hz) 162.7 (d, J
F
¼246 Hz); B NMR (160 MHz, MeOD)
d
þ28.5;
B NMR (160 MHz, CDCl
3
)
d
EM (ESI): m/z (Mþ) calcd for C
8
H
11BO
2
F 169.08972, found 169.08307.
12 2
C H18BO 205.14448, found 205.13944.
1
4
.4.6. 3-Fluoro-4-methylphenylboronic acid (5f). Off-white solid, H
4.4.17. 2-(4-methoxyphenyl)-5,5-dimethyl-1,3,2-dioxaborinane
6
b,7a,20a
1
NMR (500 MHz, MeOH-d
s, 1H), 7.35 (s, 1H); 13C NMR (125 MHz, MeOH-d
) d
4
4
)
d
2.21 (s, 3H), 7.13 (t, 1H, J¼7.0 Hz), 7.29
14.7, 120.7,
¼242); B NMR (160 MHz, MeOH-d
þ28.8; EM (ESI): m/z (Mþ) calcd for C 13BFO 183.10495, found
(12a)
3
. Yellow Oil, H NMR (500 MHz, CDCl ) d 1.02 (s, 6H),
(
3.76 (s, 4H), 3.80 (s, 3H), 6.92 (d, 2H, J¼8.5 Hz), 7.83 (d, 2H, J¼9 Hz);
11
13
120.8, 130.6, 132.1, 162.6 (d, J
F
4
)
C NMR (125 MHz, CDCl
3
)
d
22.0, 32.0, 55.1, 72.4,113.4,128.9, 132.4,
135.9,162.1; B NMR (160 MHz, CDCl
þ27.0; EM (ESI): m/z (Mþ)
calcd for C12 221.12795, found 221.13435.
11
d
9
H
2
3
) d
183.09872.
H18BO
3
4
.4.7. 3-Cyanophenylboronic acid (5g)22. Off-white solid, 1H NMR
7.45 (t, 1H, J¼8.0 Hz), 7.67 (d, 1H, J¼8.0 Hz)
.96 (m, 1H); 1 C NMR (125 MHz, MeOH-d
111.2, 118.7, 128.1,
þ27.6.
4.4.18. 2-(4-methylphenyl)-5,5-dimethyl-1,3,2-dioxaborinane
6
b,7a,20a
1
(
500 MHz, MeOH-d
4
)
d
(12b)
3
. Yellow Oil, H NMR (500 MHz, CDCl ) d 1.10 (s, 6H),
3
13
7
1
4
)
d
2.41 (s, 3H), 3.80 (s, 4H), 7.23 (d, J¼7.5 Hz), 7.78 (d, 2H, J¼5.0 Hz);
C
B
33.0, 137.1, 137.9; 11B NMR (160 MHz, MeOH-d
)
d
NMR (125 MHz, CDCl
NMR (160 MHz, CDCl
12 2
C H18BO 205.14448, found 205.13944.
11
4
3
) d 21.7, 22.0, 31.9, 72.4, 128.5, 134.1, 140.8;
3
)
d
þ27.1; EM (ESI): m/z (Mþ) calcd for
21
1
4.4.8. Thiopen-2-ylboronic acid (5h) (7g) . Off-white solid, H NMR
13
(
4
500 MHz, MeOH-d ) d 7.13 (s, 1H), 7.59 (s, 2H); C NMR (125 MHz,
11
MeOH-d
4
) 127.4, 130.9; B NMR (160 MHz, MeOH-d
4
)
d
þ26.8; EM
4.4.19. 5,5-dimethyl-2-(thiophen-2-yl)-1,3,2-dioxaborinane
6
b,7a,20a
1
(
ESI): m/z (Mþ) calcd for C
H
4 5
BO S 157.05865, found 157.04891.
2
(12c)
(
3
. Yellow Oil, H NMR (500 MHz, CDCl ) d1.04(s, 6H), 3.77
13
s, 4H), 7.20 (s,1H), 7.58 (s,1H), 7.63(s,1H); C NMR (125MHz, CDCl )
d 21.9, 72.5,128.2,131.5,135.8; B NMR (160MHz, CDCl ) d
3
(ESI): m/z (Mþ) calcd for C
3
.4.9. (E)-Styrylboronic acid (7f) . Off-white solid, 1H NMR
6.18 (d, 1H, J¼18.0 Hz), 7e7.3 (m, 5H) 7.42
126.6, 127.6,
2
1
11
þ25.5;EM
9 2
H14BO S 197.08817, found 197.08021.
4
(
500 MHz, MeOH-d
4
)
d
1
3
(
1
d, 1H, J¼7.0 Hz); C NMR (125 MHz, MeOH-d
4
) d
11
27.9, 128.3, 137.8, 146.9; B NMR (160 MHz, MeOH-d
4
)
d
þ32.4;
References and notes
EM (ESI): m/z (Mþ) calcd for C
H
8 9
BNaO
2
171.05905, found
171.05878.
1. (a) Miyaura, N.; Yanagi, T.; Suzuki, A. Synth. Commun. 1981, 11, 513; (b) Miyaura,
N.; Suzuki, A. Chem. Rev. 1995, 95, 2457; (c) Ishihara, K.; Yamamoto, H. Eur. J. Org.
Chem. 1999, 527; (d) Matteson, D. S. In Stereodirected Synthesis with Organo-
boranes; Hafner, K., Rees, C. W., Trost, B. M., Lehn, J. M., Von Rague Schleyer, P.,
Eds.; Springer: Heidelberg, 1995; (e) Bertounesque, E.; Florent, J. C.; Monneret,
C. Synthesis 1991, 4, 270; (f) Ravichandran, K.; Kerdesky, F. A. J.; Cava, M. J. Org.
Chem. 1986, 51, 2044; (g) Rho, Y. S.; Kim, S. Y.; Cho, I.; Kang, H. S.; Yoo, D. J.;
Cheong, C. Bull. Korean Chem. Soc. 1998, 19, 1059; (h) Eagon, S.; Kim, J.; Yan, K.;
Haddenham, D.; Singaram, B. Tetrahedron Lett. 2007, 48, 9025; (i) Cowden, C. J.;
Paterson, I. Org. React. 1997, 51, 38.
2
1
1
4
.4.10. Thiophen-3-ylboronic acid (7h) . Off-white solid, H NMR
13
(
(
500 MHz, MeOH-d
125 MHz, MeOH-d
þ27.0.
4
) d 7.28 (s, 1H) 7.36 (s, 1H) 7.84 (s, 1H); C NMR
4
) d 124.6,127.3,131.6,134.3; B NMR (160 MHz,
11
4
MeOH-d ) d
.4.11. 3,4-Dimethylphenylboronic acid (9d). Off-white solid, 1
4
H
NMR (500 MHz, CDCl
s, 2H); 13C NMR (125 MHz, CDCl
) d
3
3
)
d
2.61 (s, 3H), 2.65 (s, 3H), 7.54 (s, 1H), 8.24
20.0, 20.5, 128.2, 129.7, 133.7,
þ29.3; EM (ESI): m/
8 2
H11BNaO 173.07764, found 173.07443.
2. Boronic Acids; Hall, D. G., Ed.; Wiley-VCH: Germany, 2005.
3
. (a) Myung, J.; Kim, K. B.; Crews, C. M. Med. Res. Rev. 2001, 21, 245; (b) Soloway, A.
H.; Tjarks, W.; Barnum, B. A.; Rong, F. G.; Barth, R. F.; Codogni, I. M.; Wilson, J. G.
Chem. Rev. 1998, 98, 1515; (c) Kitano, S.; Koyama, Y.; Kataoka, K.; Okano, T.;
Sakurai, Y. J. Controlled Release 1992,19,161; (d) Riggs, J. A.; Hossler, K. A.; Smith, B.
D.; Karpa, M. J.; Griffin, G.; Duggan, P. J. Tetrahedron Lett.1996, 37, 6303; (e) James,
T. D.; Sandanayake, K. R. A. S.; Shinkai, S. Angew. Chem., Int. Ed. 1996, 35, 1911; (f)
Sugasaki, A.; Sugiyasu, K.; Ikeda, M.; Takeuchi, M.; Shinkai, S. J. Am. Chem. Soc.
(
1
11
36.3, 137.0, 141.8; B NMR (160 MHz, MeOH)
d
z (Mþ) calcd for C
2
1
1
4
.4.12. 4-Chlorophenylboronic acid (9f) . Off-white solid, H NMR
13
(
500 MHz, MeOD)
d
5.70 (d, 2H, J¼7.0 Hz), 6.04 (d, 2H, J¼6.5 Hz);
C
2001, 123, 10239; (g) Yang, W. Q.; Gao, X. M.; Karnati, V. V. R.; Ni, W. J.; Wang, B.;
1
1
NMR (125 MHz, MeOD)
d
d
125.7, 133.4; B NMR (160 MHz, MeOD)
Hooks, W. B.; Carson, J.; Weston, B. Bioorg. Med. Chem. Lett. 2002, 12, 2175.
. (a) Brown, H. C.; Cole, T. E. Organometallics 1983, 2, 1316; (b) Brown, H. C.; Bhat,
N. G.; Srebnik, M. Tetrahedron Lett. 1988, 29, 2631; (c) Brown, H. C.; Rangaish-
envi, M. V. Tetrahedron Lett. 1990, 49, 7113; (d) Matteson, D. S.; Liedtke, J. D.
J. Am. Chem. Soc. 1965, 87, 1526.
5. (a) Khotinsky, E.; Melamed, M. Ber. 1909, 54, 2784; (b) Gilman, H.; Vernon, C.
J. Am. Chem. Soc. 1926, 48, 1063.
. (a) Ishiyama, T.; Miyaura, N. Chem. Rec. 2004, 3, 271; (b) Ishiyama, T.; Murata,
M.; Miyaura, N. J. Org. Chem. 1995, 60, 7508.
4
þ30.4; EM (ESI): m/z (Mþ) calcd for C
6
H
11BClO
2
185.04943, found
185.05351.
2
1
1
4
.4.13. 4-Cyanophenylboronic acid (9h) . Off-white solid, H NMR
13
(
500 MHz, MeOD)
d
7.04 (d, 2H, J¼8.0 Hz), 7.23 (d, 2H, J¼8.5 Hz);
C
6
11
NMR (125 MHz, MeOD)
d
116.8, 129.0, 132.4; B NMR (160 MHz,