M. Pucheault, S. Darses, J.-P. Gen eˆ t
FULL PAPER
was carried out on silica-gel plates (Merck F254) and spots were
detected with UV light.
and 6.6 Hz, 1 H), 6.39 (d, J ϭ 15.9 Hz, 1 H), 7.12 (d, J ϭ 8 Hz, 2
1
3
H), 7.25 (d, J ϭ 8 Hz, 2 H) ppm. C NMR (50 MHz, CDCl
3
):
δ ϭ 21.0, 24.9, 31.4, 41.2, 41.8, 47.4, 125.9, 128.8, 129.2, 131.8,
GC analyses were performed on a HewlettϪPackard 5890 instru-
ment equipped with a J&W Scientific DB-1701 capillary column
ϩ·
1
1
34.2, 137.0, 210.8 ppm. MS (70 eV): m/z (%) ϭ 214 (19) [M ],
05 (100).
(15 m, Ø ϭ 0.25 µm), using an ionisation flame detector. Chiral
HPLC analysis were conducted with Waters 600 system, using
(R)-3-[2-(4-Methylphenyl)vinyl]cycloheptanone (3hb): Colourless oil
Daicel Chiralcel chiral stationary phase columns: OD-H hexane/2- (85 mg) obtained from 1h (0.5 mmol) and 2b (1 mmol) in 74% yield
1
propanol 98:2 (3ba, 3bd, 3hb), OD-H hexane/2-propanol 90:10
3ad, 3cb), OJ hexane/2-propanol 90:10 (3ca), OJ hexane/2-pro-
according to the general procedure. H NMR (200 MHz, CDCl ):
3
(
δ ϭ 1.4Ϫ2.8 (m, 14 H), 6.10 (dd, J ϭ 15.9 Hz and 6.7 Hz, 1 H),
panol 98:2 (3ab), AD hexane/2-propanol 98:2 (3da), AD hexane/2-
propanol 95:5 (3ea), AS-H hexane/2-propanol 98:2 (3aa, 3ac, 3ae,
6.37 (d, J ϭ 15.9 Hz, 1 H), 7.11 (d, J ϭ 8 Hz, 2 H), 7.21 (d, J ϭ
1
3
8 Hz, 2 H) ppm. C NMR (50 MHz, CDCl ): δ ϭ 21.0, 24.0, 28.3,
3
3
fa, 3gd, 3ha), AS-H hexane/2-propanol 90:10 (3ec). Enantiomeric 37.1, 39.3, 44.0, 49.4, 125.9, 128.2, 129.1, 133.2, 134.4, 136.9,
ϩ·
excesses of compound 3ia were determined by chiral GC analysis:
Hydrodex -β-6-TBDM column (25 m, Ø ϭ 0.25 mm), at 90 °C
and 1.3 mL·min
213.5 ppm. MS (70 eV): m/z (%) ϭ 228 (23) [M ], 129 (62), 118
(65), 105 (100).
Ϫ1
.
Potassium organotrifluoroborates[16c] and [Rh(cod)
prepared according to published procedures. Toluene was freshly
distilled from CaH
][PF
6
][27] were
2
Acknowledgments
2
.
We are grateful to Dr. R. Schmidt (Hoffmann La Roche) for the
generous gift of MeO-biphep chiral ligand. M. Pucheault thanks
the Ecole Normale Sup e´ rieure of Paris for a grant.
Typical Procedure for the 1,4-Addition of Potassium Aryl- and Alk-
enyltrifluoroborates to Enones: A mixture of potassium organotri-
fluoroborate (number of equivalents indicated in the table),
2 6
[Rh(cod) ][PF ] (7.0 mg, 3 mol %), and (R)- or (S)-binap (10.3 mg,
3
.3 mol %) were placed in a flask and then a degassed toluene/water
[
1]
[1a]
mixture (2 mL/0.5 mL) was added at room temperature followed by
the enone (0.5 mmol). The flask was heated in a preheated oil bath
at 105Ϫ110 °C and the mixture was stirred until completion of the
reaction (followed by GC analysis). After filtration through celite
Reviews:
171Ϫ196. [ M. P. Sibi, S. Manyem, Tetrahedron 2000, 56,
033Ϫ8061.
M. Sakai, H. Hayashi, N. Miyaura, Organometallics 1997, 16,
229Ϫ4231.
N. Krause, A. Hoffmann-Röder, Synthesis 2001,
1b]
8
[
[
2]
3]
4
2 2
(eluting with CH Cl ), the solvent was removed under reduced
Y. Takaya, M. Ogasawara, T. Hayashi, M. Sakai, N. Miyaura,
J. Am. Chem. Soc. 1998, 120, 5579Ϫ5580.
pressure. Purification by chromatography through silica gel af-
forded analytically pure product.
[4]
For a review: T. Hayashi, Synlett 2001, 879Ϫ887. For a study
of the mechanism: T. Hayashi, M. Takahashi, Y. Takaya, M.
Ogasawara, J. Am. Chem. Soc. 2002, 124, 5052Ϫ5058.
(R)-3-Phenyldecan-2-one (3ae): Light yellow oil (111 mg) obtained
from 1a (0.5 mmol) and 2e (1 mmol) in 95% yield according to the
general procedure. H NMR (200 MHz, CDCl
H), 1.1Ϫ1.4 (m, 9 H), 2.03 (s, 3 H), 2.73 (d, J ϭ 7.2 Hz, 2 H),
[5] [5a]
Y. Takaya, M. Ogasawara, T. Hayashi, Tetrahedron Lett.
1
): δ ϭ 0.7Ϫ1 (m, 4
[5b]
3
1
998, 39, 8479Ϫ8482.
Y. Takaya, M. Ogasawara, T. Haya-
[5c]
shi, Tetrahedron Lett. 1999, 40, 6957Ϫ6961.
Y. Ta k ay a , M .
7
2
1
4
.1Ϫ7.4 (m, 5 H) ppm. 13C NMR (50 MHz, CDCl
3
): δ ϭ 13.9,
Ogasawara, T. Hayashi, Chirality 2000, 12, 469Ϫ471.
[6] [6a]
2.5, 27.2, 29.1, 30.5, 31.6, 36.4, 41.2, 50.8, 126.2, 127.4, 128.3,
44.5, 207.9 ppm. MS (70 eV): m/z (%) ϭ 232 (2) [M ], 174 (18),
Y. Takaya, T. Senda, H. Kurushima, M. Ogasawara, T. Hay-
ashi, Tetrahedron: Asymmetry 1999, 10, 4047Ϫ4056. [ S. Sak-
uma, M. Sakai, R. Itooka, N. Miyaura, J. Org. Chem. 2000,
6b]
ϩ·
3 (100).
6
5, 5951Ϫ5955.
[
[
7] [7a]
T. Senda, M. Ogasawara, T. Hayashi, J. Org. Chem. 2001,
(
R)-4-Thiophen-3-ylnonan-2-one (3gd): Light yellow oil (94 mg) ob-
tained from 1g (0.5 mmol) and 2d (1 mmol) in 84% yield according
to the general procedure. 1H NMR (200 MHz, CDCl
): δ ϭ
.7Ϫ0.9 (m, 3 H), 1.1Ϫ1.4 (m, 6 H), 1.4Ϫ1.7 (m, 2 H), 2.03 (s, 3
H), 2.68 (d, J ϭ 14.1 Hz, 2 H), 3.28 (m, 1 H), 6.90Ϫ6.97 (m, 2 H),
7b]
6
6, 6852Ϫ6856. [ S. Sakuma, N. Miyaura, J. Org. Chem.
2001, 66, 8944Ϫ8946.
T. Hayashi, T. Senda, Y. Takaya, M. Ogasawara, J. Am. Chem.
Soc. 1999, 121, 11591Ϫ11592.
T. Hayashi, T. Senda, M. Ogasawara, J. Am. Chem. Soc. 2000,
22, 10716Ϫ10717.
M. Kuriyama, K. Tomioka, Tetrahedron Lett. 2001, 42,
3
8]
0
[9]
7
2
2
.23Ϫ7.3 (m, 1 H) ppm. 13C NMR (50 MHz, CDCl
3
): δ ϭ 13.8,
1
[10]
2.3, 26.7, 30.3, 31.5, 36.0, 36.3, 50.4, 119.9, 125.3, 126.3, 145.2,
ϩ·
07.8 ppm. MS (70 eV): m/z (%) ϭ 224 (20) [M ], 181 (26), 125
921Ϫ923.
[11]
(40), 43 (100).
M. T. Reetz, D. Moulin, A. Gosberg, Org. Lett. 2001, 3,
083Ϫ4085.
R. Itooka, Y. Iguchi, N. Miyaura, Chem. Lett. 2001, 722Ϫ723.
R. Amengual, V. Michelet, J.-P. Genet, Tetrahedron Lett. 2002,
in press.
It has been shown recently that the use of chiral binol-based
diphosphonites allows the use of only a slight excess (1.2
4
[
[
12]
13]
(S)-3-(3-Chlorophenyl)decan-2-one (3be): Colourless oil (126 mg)
obtained from 1b (0.5 mmol) and 2e (1 mmol) in 95% yield accord-
ing to the general procedure. 1H NMR (200 MHz, CDCl
): δ ϭ
.7Ϫ0.9 (m, 3 H), 1.1Ϫ1.4 (m, 8 H), 1.4Ϫ1.8 (m, 2 H), 2.05 (s, 3
H), 2.72 (d, J ϭ 14.2 Hz, 2 H), 3.12 (m, 1 H), 7.0Ϫ7.4 (m, 4 H)
ppm. 13C NMR (50 MHz, CDCl
): δ ϭ 13.8, 22.3, 27.0, 28.9, 30.4,
1.4, 36.1, 40.6, 50.3, 125.6, 126.3, 127.3, 129.4, 134.0, 146.7,
3
[14]
0
[
11]
equiv.) of the boronic acid in the addition to enones: see ref.
3
[15]
In the 1,4-addition of organoboron compounds, it has been
shown that in situ generated organoborates [RB(OMe) Li] can
be used in place of organoboronic acids to avoid their isola-
Another alternative is the use of boronic esters, al-
though a base is needed in this case.
S. Darses, J.-P. Genet, J.-L. Brayer, J.-P. Demoute, Tetrahed-
ron Lett. 1997, 38, 4393Ϫ4396.
P. Genet, Tetrahedron Lett. 1998, 39, 5045Ϫ5048.
3
2
3
ϩ·
07.0 ppm. MS (70 eV): m/z (%) ϭ 266 (3) [M ], 208 (35), 43 (100).
tion.[
5b,6a]
(R)-3-[2-(4-Methylphenyl)vinyl]cyclohexanone (3ha): White solid
[5a,7b]
(100 mg) obtained from 1h (0.5 mmol) and 2a (1.5 mmol) in 93%
[16] [16a]
1
[16b]
yield according to the general procedure. m.p. 94Ϫ95 °C. H NMR
S. Darses, G. Michaud, J.-
[
16c]
(200 MHz, CDCl
3
): δ ϭ 1.5Ϫ2.8 (m, 12 H), 6.1 (dd, J ϭ 15.9 Hz
S.
3556
Eur. J. Org. Chem. 2002, 3552Ϫ3557