1794
R. Amengual et al.
LETTER
(2) McCarthy, M.; Guiry, P. J. Tetrahedron 2001, 57, 3809.
(3) Cornils, B.; Herrmann, W. A. In Aqueous-Phase
Organometallic Catalysis; Wiley-VCH: New York, 1998.
(4) (a) Sinou, D. Adv. Synth. Catal. 2002, 344, 221.
(b) Lindström, U. M. Chem. Rev. 2002, 102, 2751. (c) Li,
C. J.; Chan, T. K. Organic Reactions in Aqueous Media;
JohnWiley & Son: New York, 1997. (d) Organic Synthesis
in Water; Grieco, P. A., Ed.; Blacky Academic and
Professional: London, 1998.
(5) (a) Genêt, J.-P. Reductions in Organic Synthesis, A.C.S.
Symposium Series 641; ACS: New York, 1996, 31–51.
(b) Ratovelomanana–Vidal, V.; Genêt, J.-P. J. Organomet.
Chem. 1998, 567, 163. (c) Ratovelomanana-Vidal, V.;
Genêt, J.-P. Can. J. Chem. 2000, 78, 846.
(13) (a) Pucheault, M.; Darses, S.; Genêt, J.-P. Tetrahedron Lett.
2002, 43, 6155. (b) Pucheault, M.; Darses, S.; Genêt, J.-P.
Eur. J. Org. Chem. 2002, in press.
(14) (a) Takaya, Y.; Ogasawara, M.; Hayashi, T. Tetrahedron
Lett. 1998, 39, 8479. (b) Takaya, Y.; Senda, T.; Kurushima,
H.; Ogasawara, M.; Hayashi, T. Tetrahedron: Asymmetry
1999, 10, 4047. (c) Takaya, Y.; Ogasawara, M.; Hayashi, T.
Tetrahedron Lett. 1999, 40, 6957. (d) Takaya, Y.;
Ogasawara, M.; Hayashi, T. Chirality 2000, 12, 469.
(e) Sakuma, S.; Miyaura, N. J. Org. Chem. 2001, 66, 6852.
(15) For recent reviews on asymmetric 1,4-addition, see:
(a) Hayashi, T. Synlett 2001, 879. (b) Krause, N.;
Hoffmann-Röder, A. Synthesis 2001, 171. (c) Sibi, M. P.;
Manyem, S. Tetrahedron 2000, 56, 8033.
(6) For recent reviews on Pd-catalyzed reactions, see:
(a) Genêt, J.-P.; Savignac, M. J. Organomet. Chem. 1999,
576, 305. (b) Genêt, J.-P.; Savignac, M.; Lemaire-Audoire,
S. In IUPAC Monographs: Chemistry for the 21st Century,
Transition Metal Catalysed Reactions; Murahashi, S.-I.;
Davies, S. G., Eds.; Blackwell: London, 1999, 55.
(7) (a) Michelet, V.; Galland, J.-C.; Charruault, L.; Savignac,
M.; Genêt, J.-P. Org. Lett. 2001, 3, 2065. (b) Dupuis, C.;
Adiey, K.; Charruault, L.; Michelet, V.; Savignac, M.;
Genêt, J.-P. Tetrahedron Lett. 2001, 42, 6523.
(16) Reetz, M.; Moulin, D.; Gosberg, A. Org. Lett. 2001, 3, 4083.
(17) Kuriyama, M.; Tomioka, K. Tetrahedron Lett. 2001, 42,
921.
(18) Hayashi, T.; Takahashi, M.; Takaya, Y.; Ogasawara, M. J.
Am. Chem. Soc. 2002, 124, 5052.
(19) Unpublished results (E. Genin, D.E.A. Multinational de
Chimie Moléculaire de l’Ecole Polytechnique).
(20) Ethylene glycol, purchased from Acros, contains 0.05%
water and was used without further treatment.
(21) Typical procedure : A solution of Rh(acac)(C2H4)2 (1.3 mg,
0.006 mmol) and (R)-Digm-BINAP (5.0 mg, 0.006 mmol) in
degassed ethyleneglycol (1.0 mL) was stirred under argon
for 15 minutes at room temperature, then phenylboronic acid
(122 mg, 1 mmol), sodium carbonate (43 mg, 0.4 mmol) and
cyclohexenone (20 L, 0.2 mmol) were successively added.
The heterogeneous mixture was stirred at 100 °C until
completion of the reaction (gas chromatography). After
cooling at room temperature the solution was extracted two
times with ethyl acetate. The combined organic layers were
filtered on a short pad of silica gel and evaporated under
reduced pressure. A slight yellow oil (34 mg, 100%) was
obtained. The purity of the compound was checked by gas
chromatography and 1H NMR. The enantiomeric excess was
determined by HPLC (Daicel Chiralcel OD-H, hexane/i-
PrOH = 98:2, 1 mL/min).
(8) Amengual, R.; Genin, E.; Michelet, V.; Savignac, M.; Genêt,
J.-P. Adv. Synth. Catal. 2002, 344, 393.
(9) (a) Guerreiro, P.; Ratovelomanana-Vidal, V.; Genêt, J.-P.;
Dellis, P. Tetrahedron Lett. 2001, 42, 3423. (b) Guerreiro,
P.; Genêt, J.-P.; Dellis, P. French patent, 99 15217, 1999.
(c) For the synthesis of (R)-Diam-BINAP, see: Lemaire, M.;
ter Halle, R.; Samson, E.; Colasson, B.; Spagnol, M. French
Patent 99 02510, 1999. (d) See also: ter Halle, R.; Colasson,
B.; Schulz, E.; Spagnol, M.; Lemaire, M. Tetrahedron Lett.
2000, 41, 643.
(10) Amengual, R.; Michelet, V.; Genêt, J.-P. Tetrahedron Lett.
2002, 43, 5905.
(11) Takaya, Y.; Ogasawara, M.; Hayashi, T.; Sakai, M.;
Miyaura, N. J. Am. Chem. Soc. 1998, 120, 5579.
(12) (a) Sakuma, S.; Sakai, M.; Itooka, R.; Miyaura, N. J. Org.
Chem. 2000, 65, 5951. (b) Hayashi, T.; Senda, T.; Takaya,
Y.; Ogasawara, M. J. Am. Chem. Soc. 1999, 121, 11591.
(c) Sakuma, S.; Miyaura, N. J. Org. Chem. 2001, 66, 8944.
(d) Hayashi, T.; Senda, T.; Ogasawara, M. J. Am. Chem. Soc.
2000, 122, 10716.
Synlett 2002, No. 11, 1791–1794 ISSN 0936-5214 © Thieme Stuttgart · New York