J. A. Soderquist et al. / Tetrahedron Letters 45 (2004) 5541–5543
5543
5
. (a) Brown, H. C.; Carlson, B. A.; Prager, R. H. J. Am.
Chem. Soc. 1971, 93, 2070–2071; (b) Brown, H. C.;
Carlson, B. A. J. Org. Chem. 1973, 38, 2422–2424.
14. To a stirred solution of 1a (2.71 g, 10.8 mmol) and a,a-
dichloromethyl methyl ether (1.37 g, 1.08 mL, 11.9 mmol)
in THF (11 mL) at 0 °C, a lithium tert-butoxide solution
prepared from tert-butanol (4.00 g, 54.0 mmol) and n-BuLi
(22.3mL of 2.42 M, 54.0 mmol) was added dropwise via
cannula. After the addition, the reaction mixture was
allowed to reach room temperature, which produced a
white precipitate (Li salt). After 1 h at room temperature,
the solvents were removed in vacuo. Ethanol (43mL) and
solid NaOH (5.20 g, 130 mmol) were added, followed by
the dropwise addition of hydrogen peroxide (21.6 mL of
10 M, 216 mmol) at 0 °C. The mixture was heated at ca.
6
. Brown, H. C.; Katz, J. J.; Carlson, B. A. J. Org. Chem.
1
973, 38, 3968–3970.
. Carlson, B. A.; Brown, H. C. J. Am. Chem. Soc. 1973, 95,
876–6877.
7
6
8
9
. Brown, H. C.; Imai, T. J. Org. Chem. 1984, 49, 892–898.
. (a) Soderquist, J. A.; Najafi, M. R. J. Org. Chem. 1986, 51,
1
330–1336; (b) Soderquist, J. A.; Anderson, C. L. Tetra-
hedron Lett. 1986, 27, 3961–3962.
0. (a) Soderquist, J. A.; Santiago, B. Tetrahedron Lett. 1990,
1, 5541–5542; (b) Matos, K.; Soderquist, J. A. J. Org.
Chem. 1998, 63, 461–470.
1. Wenger, W.; Vasella, A. Helv. Chim. Acta 2000, 83, 1542–
560.
2. Soderquist, J. A.; Ramos, J.; Matos, K. Tetrahedron Lett.
997, 38, 6639–6642.
3. Representative procedure for the preparation of 1. To a
solution of 9-BBN-H (9.76 g, 80.0 mmol) in THF (80 mL),
1
3
50 °C for 3h to destroy the excess of H
2 2
O , cooled to room
temperature, acidified with 50% aqueous HCl, saturated
with sodium chloride, and extracted with ether
(2 · 30 mL). The combined organic layers were extracted
with a aqueous saturated sodium bicarbonate solution (3·
equal volume). These extracts were acidified with 50%
aqueous HCl, saturated with NaClðsÞ, and extracted with
ether (2· equal volume). The combined extracts were dried
1
1
1
1
1
1
mixture was allowed to stir for 4 h with complete reaction
-octene (8.96 g, 80.0 mmol) was added. The reaction
4
over anhydrous MgSO and the solvents were removed in
vacuo to give nonanoic acid (2a) containing trace quan-
tities of cis-1,5-cyclooctanediol. Vacuum distillation affor-
1
1
being corroborated by B NMR. Subsequently, the
solution was cooled to 0 °C and a solution of TMANO
1
7
ded 1.42 g (83%) of 2a (bp 82–83 °C, 1 mmHg; lit. bp
1
(
6.04 g, 80.0 mmol) in CHCl
3
(40 mL) was added dropwise
252–253 °C, 760 mmHg). H NMR (CDCl
3
) d 0.97 (t,
via cannula. The solvents were removed under reduced
pressure and the oily residue was diluted in hexanes. The
hexanes solution was filtered under nitrogen through silica
J ¼ 7:0 Hz, 3H), 1.20–1.58 (m, 12H), 2.18 (t, J ¼ 7:5 Hz,
1
3
2H), 10.33 (br s, 1H) ppm. C NMR (CDCl
24.7, 29.0, 29.2, 29.3, 31.9, 34.0, 180.5 ppm.
3
) d 14.0, 22.8,
gel. The filtrate was concentrated to produce 19.15 g (96%)
1
15. Unpublished studies with Dr. Peter Baran (UPR-RP).
16. (a) Soderquist, J. A.; Shiau, F.-Y.; Lemesh, R. A. J. Org.
Chem. 1984, 49, 2565–2569; (b) Soderquist, J. A.; Negron,
A. J. Org. Chem. 1989, 54, 2462–2464.
17. The Merck Index: An Encyclopedia of Chemicals, Drugs
and Biologicals, 13th ed.; O’Neil, M. J., Ed.; Merck
Research Laboratories: Whitehouse, NJ, 2001; p 7141.
of borinate 1a. H NMR (300 MHz, C
6
D
6
) d 0.87 (q,
J ¼ 7:6 Hz, 3H), 1.03 (t, J ¼ 7:6 Hz, 2H), 1.27–1.34 (m,
1
3
1
(
(
6H), 1.55–1.66 (m, 9H), 4.54 (m, 1H) ppm. C NMR
75 MHz, C ) d 14.4, 22.7, 23.1, 24.3 (br s), 24.5, 25.8
br s), 26.4, 29.9, 30.2, 32.1, 32.4, 33.3, 73.1 ppm.
) d 53.9 (s) ppm.
6
D
6
1
1
B
6 6
NMR (96 MHz, C D