R. A. Batey, T. D. Quach / Tetrahedron Letters 42 (2001) 9099–9103
9103
1
3
Acknowledgements
1.40–1.18 (16H, m), 0.89 (12H, t, J=7.0 Hz); C NMR
(
1
CDCl , 75 MHz) l 131.6, 126.4, 125.3, 57.6, 23.3, 19.1,
3
3.3 (one signal absent); B NMR (CDCl , 160 MHz) l
3.30 (br s); F NMR (CDCl , 282 MHz) l −142.03 (br
11
3
19
T.D.Q. gratefully acknowledges the receipt of an
Ontario Graduate Scholarship in Science and Technol-
ogy (OGSST), and thanks Dr. A. N. Thadani for his
advice in working with trifluoroborate salts. We would
like to thank Dr. A. J. Lough for his work in X-ray
crystallography, and Dr. A. B. Young for mass spectro-
metric analysis.
3
s); IR (film) w 3449, 2964, 2876, 1636, 1487, 1431, 1382,
−
1
1269, 1192, 1071, 950, 908, 751, 706, 598 cm ; LRMS
(FAB): m/z=145 (100), 144 (25), 91 (22), 34 (10); HRMS
(FAB): m/z calcd. for (C H BF )=145.0436, found=
−
3
6
5
145.0449.
0. An alternative synthesis of nBu N PhBF from PhBF2
+
−
3
1
4
and TBAF has been reported. See: Wang, C.; Mo, Y.;
Jang, M.; Janzen, A. F. Can. J. Chem. 1993, 71, 525–528.
1. Hughes, M. P.; Smith, B. D. J. Org. Chem. 1997, 62,
References
1
1
4492–4499.
1
2
. (a) Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457–
2. (a) Quach, T. D.; Batey, R. A.; Lough, A. J. Acta
Crystallogr., Sect. E: Struct. Rep. Online 2001, E57,
o688–o689; (b) Quach, T. D.; Batey, R. A.; Lough, A. J.
Acta Crystallogr., Sect. E: Struct. Rep. Online 2001, E57,
m320–m321.
2
1
483; (b) Suzuki, A. J. Organomet. Chem. 1999, 576,
47–168.
. (a) Vedejs, E.; Fields, S. C.; Schrimpf, M. R. J. Am.
Chem. Soc. 1993, 115, 11612–11613; (b) Vedejs, E.;
Fields, S. C.; Hayashi, R.; Hitchcock, S. R.; Powell, D.
R.; Schrimpf, M. R. J. Am. Chem. Soc. 1999, 121,
460–2470.
. (a) Batey, R. A.; Thadani, A. N.; Smil, D. V. Org. Lett.
999, 1, 1683–1686; (b) Batey, R. A.; Thadani, A. N.;
Smil, D. V. Tetrahedron Lett. 1999, 40, 4289–4292; (c)
Batey, R. A.; Thadani, A. N.; Smil, D. V.; Lough, A. J.
Synthesis 2000, 990–998.
. Wright, S. W.; Hageman, D. L.; McClure, L. D. J. Org.
Chem. 1994, 59, 6095–6097.
. Darses, S.; Jeffery, T.; Brayer, J.-L.; Demoute, J.-P.;
Gen eˆ t, J.-P. Bull. Soc. Chim. Fr. 1996, 133, 1095–1102.
. Littke, A. F.; Dai, C.; Fu, G. C. J. Am. Chem. Soc. 2000,
1
3. Representative procedure as used for the synthesis of 6f:
+
−
nBu N C H CHꢁCHBF
(0.53 g, 1.25 mmol), 4-
4
6
13
3
2
BrC H COCH (0.20 g, 1.00 mmol), dppb (21 mg, 0.050
6
4
3
3
mmol) and Cs CO (0.41 g, 1.25 mmol) were suspended
2
3
1
in DME (5 mL). Water (5 mL) was then added to the
stirred reaction mixture, along with the Pd(OAc) catalyst
2
(
2
11 mg, 0.050 mmol). The reaction was stirred at 50°C for
4 h, then transferred to a separatory funnel, diluted with
4
5
6
water (30 mL), and extracted with CH Cl2 (3×10 mL).
2
The combined organic layers were dried (MgSO4),
filtered, and concentrated in vacuo to afford the crude
product mixture. The product (6f) was isolated by
column chromatography (eluting with hexanes:EtOAc
1
22, 4020–4028.
9
1
:1ꢀ3:1) as an oil (0.20 g, 0.87 mmol, 87%).
-(4-Acetylphenyl)-1-octene (6f): H NMR (CDCl , 300
7
8
. Molander, G. A.; Ito, T. Org. Lett. 2001, 3, 393–396.
. Acylamino difluoroborane analogues of amino acids have
been synthesized by treating the corresponding boronic
acids with an excess of HF. See: Kinder, D. H.; Katzenel-
lenbogen, J. A. J. Med. Chem. 1985, 28, 1917–1925.
. Representative procedure as used for the synthesis of 1e:
1
3
MHz) l 7.87 (2H, d, J=8.5 Hz), 7.79 (2H, d, J=8.5 Hz),
6
1
.44–6.30 (2H, m), 2.55 (3H, s), 2.26–2.18 (2H, m),
.52–1.24 (8H, m), 0.89 (3H, t, J=7.5 Hz); C NMR
13
(
CDCl , 75 MHz) l 197.6, 142.8, 135.5, 134.6, 129.0,
3
9
128.8, 126.0, 33.3, 31.8, 29.2, 29.0, 26.6, 22.7, 14.2; IR
To a solution of PhB(OH) (0.52 g, 4.27 mmol) in MeOH
2
(
film) w 2926, 2855, 1682, 1648, 1602, 1563, 1466, 1410,
(
1
ca. 1 mL) was added a solution of HF (2.65 mL, 5.0 M,
3.3 mmol) via a polypropylene syringe with vigorous
stirring over 1 min at rt. The reaction mixture was then
cooled to 0°C and a solution of nBu N OH (2.76 mL,
.54 M, 4.27 mmol) was slowly added over 5 min. The
reaction was warmed to rt and stirred for another 1 h.
The biphasic reaction mixture was diluted with CH Cl2
10 mL), the layers separated, and the aqueous phase
1
7
357, 1268, 1181, 1111, 1074, 1013, 966, 855, 809, 724,
05, 592 cm ; LRMS (EI): m/z=231 (21), 230 (89), 216
−
1
+
−
(16), 215 (77), 147 (22), 146 (67), 145 (16), 134 (19), 131
100), 117 (24), 115 (37), 91 (14); HRMS (EI): m/z calcd.
4
(
1
+
for (C H O )=230.1671, found=230.1675.
16 22
1
1
1
1
4. Matos, K.; Soderquist, J. A. J. Org. Chem. 1998, 63,
2
4
61–470.
5. Bumagin, N. A.; Korolev, D. N. Tetrahedron Lett. 1999,
0, 3057–3060.
6. Haddach, M.; McCarthy, J. R. Tetrahedron Lett. 1999,
0, 3109–3112.
(
further extracted with CH Cl (3×10 mL). The combined
2
2
4
organic layers were dried (MgSO ), filtered, and concen-
trated in vacuo to afford 1.57 g of the pale yellow,
crystalline solid 1e (4.06 mmol, 95%).
Tetra-n-butylammonium phenyltrifluoroborate (1e): mp=
4°C (CH Cl ); H NMR (CDCl , 300 MHz) l 7.51 (2H,
d, J=6.5 Hz), 7.15–7.00 (3H, m), 2.90–2.80 (8H, m),
4
4
7. Kabalka, G. W.; Malladi, R. R.; Tejedor, D.; Kelley, S.
Tetrahedron Lett. 2000, 41, 999–1001.
18. Chen, H.; Deng, M. Z. Org. Lett. 2000, 2, 1649–1651.
1
7
2
2
3