√
A. Marinetti, J.-P. Genet et al.
FULL PAPER
amount of HPPh2 3.1 mmol) were added after 1, 3, and 8 h. Heating was
maintained for further 60 h. After evaporation of the solvent, the final
product was purified by flash chromatography on silica gel (cyclohexane/
ethyl acetate 95:5). Compound 5 was obtained in 60% yield (0.47 g) as a
colorless solid. M.p. 2008C; [a]D 80 (c 1, CHCl3); 31P NMR
(162 MHz, CDCl3): d À12.9 and À14.8 (JP,P 15.9 Hz); 1H NMR
(400 MHz, CDCl3, selected data): d 3.10 (s; OMe), 6.84 (d, J 7.8 Hz,
1H), 6.94 (dd, J 7.2, 2.8 Hz, 1H), ...7.34 (ddd, J 8.1, 6.2, 1.9 Hz, 1H), 7.38
(t, J 8.0 Hz, 1H), 7.78 ppm (d, J 8.4 Hz, 2H); 13C NMR (100 MHz,
CDCl3, selected data): d 54.6 (OMe), 110.6, ... 158.0 ppm (d, J 10.6 Hz,
[5] a) X. Zhang, T. Uemura, K. Matsumura, N. Sayo, H. Kumobayashi, H.
Takaya, Synlett 1994, 501; b) T. Uemura, X. Zhang, K. Matsumura, N.
Sayo, H. Kumobayashi, T. Ohta, K. Nozaki, H. Takaya, J. Org. Chem.
1996, 61, 5510.
√
[6] a) P. Bertus, P. Phansavath, V. Ratovelomanana-Vidal, J-P. Genet,
A. R. Touati, T. Homri, B. Ben Hassine, Tetrahedron: Asymmetry
√
1999, 10, 1369; b) J-P. Genet, C. Pinel, V. Ratovelomanana-Vidal, S.
Mallart, X. Pfister, L. Bischoff, M. C. Cano De Andrade, S. Darses, C.
Galopin, J. A. Laffitte, Tetrahedron: Asymmetry 1994, 5, 675; c) V.
Blandin, J-F. Carpentier, A. Mortreux, Eur. J. Org. Chem. 1999, 3421.
[7] Z. Zhang, H. Qian, J. Longmire, X. Zhang, J. Org. Chem. 2000, 65,
6223.
À
C O); HRMS (DCI): m/z: (M 1) calcd 603.2007; found 603.2001.
Asymmetric hydrogenation: typical procedure: Hydrogenation experi-
ments were performed at a 1 mmol scale, with a 1% ruthenium catalyst
which was prepared from [(cod)Ru(2-methylallyl)2] (3.2 mg) and the chiral
diphosphine 5 (7.2 mg), by addition of 2.2 equivalents of aqueous HBr
(0.16 0.18 m) in acetone.[6b] After evaporation of the solvent, the crude
residue was taken up in degassed MeOH (2 mL) or EtOH (2 mL), substrate
was added, and the reactor was placed under H2 at a given pressure and
temperature (see Table 1). All conversions were quantitative. Enantio-
meric excesses and absolute configurations were determined by chiral GC
(Entry 1: Lipodex A, flow 1 mLminÀ1, initial temperature 358C (30 min),
rate 18CminÀ1, final temperature 708C, retention times 45 (S) and 48 (R).
Entry 2: Lipodex A, flow 1 mLminÀ1, initial temperature 508C (5 min), rate
0.58CminÀ1, final temperature 708C, retention times 48.6 (S) and 49.2 (R))
or by GC on a DB1701 column, after formation of the Mosher ester (entry
3: initial temperature 1508C (60 min), rate 18CminÀ1, final temperature
1808C, retention times 88.6 (R) and 89.7 (S). Entry 4: initial temperature
2008C (10 min), rate 58CminÀ1, final temperature 2508C, retention times
18.2 (R,R), 18.7 (S,S), and 19.7 (syn isomer) min) by comparison with
known compounds.
[8] a) T. Saito, T. Yokozawa, T. Ishizaki, T. Moroi, N. Sayo, T. Miura, H.
Kumobayashi, Adv. Synth. Catal. 2001, 343, 264; b) H. Kumobayashi,
T. Miura, N. Sayo, T.; Saito, X. Zhang, Synlett 2001, 1055.
[9] B. H. Lipshutz, Z-P. Liu, F. Kayser, Tetrahedron Lett. 1994, 35, 5567.
[10] a) B. H. Lipshutz, F. Kayser, Z. P. Liu, Angew. Chem. 1994, 106, 1962;
Angew. Chem. Int. Ed. 1994, 33, 1842; b) G-Q. Lin, M. Zhong,
Tetrahedron Lett. 1997, 38, 1087.
[11] D. R. Spring, S. Krishnan, S. L. Schreiber, J. Am. Chem. Soc. 2000, 122,
5656.
[12] a) T. Sugimura, H. Yamada, S. Inoue, A. Tai, Tetrahedron: Asymmetry
1997, 8, 649; b) T. Sugimura, S. Inoue, A. Tai, Tetrahedron Lett. 1998,
39, 6487; c) T. Sugimura, T. Tei, A. Mori, T. Okuyama, A. Tai, J. Am.
Chem. Soc. 2000, 122, 2128; d) T. Sugimura, K. Hagiya, Y. Sato, T. Tei,
A. Tai, T. Okuyama, Org. Lett. 2001, 3, 37.
[13] K. J. Edgar, S. N. Falling, J. Org. Chem. 1990, 55, 5287.
[14] Iodation of resorcinol is described in: F. L. Weitl, J. Org. Chem. 1976,
41, 2044. Monomethylation has been performed through a Mitsunobu
reaction.
[15] Both enantiomers of 2,4-pentanediol are either commercially avail-
able or easily obtained in multigram scale by Ru-MeO-BIPHEP
promoted hydrogenations of 2,4-pentadedione.
[1] a) BINAP: A. Miyashita, A. Yasuda, H. Takaya, K. Toriumi, T. Ito, T.
Souchi, R. Noyori, J. Am. Chem. Soc. 1980, 102, 7932; b) H. Takaya, K.
Mashima, K. Koyano, M. Yagi, H. Kumobayashi, T. Taketomi, S.
Akutagawa, R. Noyori, J. Org. Chem. 1986, 51, 629; c) 7,7'-bis(diphe-
nylphosphanyl)-2,2'-dimethoxy-1,1'-binaphthyl: T. Horiuchi, T. Ohta,
M. Stephan, H. Takaya, Tetrahedron: Asymmetry 1994, 5, 325; d) bis-
steroidal phosphine: V. Enev, C. L. J. Ewers, M. Harre, K. Nickisch,
J. T. Mohr, J. Org. Chem. 1997, 62, 7092.
[16] The analogous Mitsunobu reactions between 2,4-pentanediol and
naphthol proceed stereospecifically, with inversion of the carbon
configuration (see ref. [12a]).
[17] a) B. H. Lipshutz, K. Siegmann, E. Garcia, F. Kayser, J. Am. Chem.
Soc. 1993, 115, 9276; b) B. H. Lipshutz, F. Kayser, N. Maullin,
Tetrahedron Lett. 1994, 35, 815.
[18] D. Cai, J. F. Payack, D. R. Bender, D. L. Hughes, T. R. Verhoeven, P. J.
Reider, J. Org. Chem. 1994, 59, 7180.
[2] a) BIPHEMP and analogues: R. Schmid, M. Cereghetti, B. Heiser, P.
Schˆnholzer, H-J. Hansen, Helv. Chim. Acta 1988, 71, 897; b) H8-
BINAP: X. Zhang, K. Mashima, K. Koyano, N. Sayo, H. Kumobaya-
shi, S. Akutagawa, H.Takaya, Tetrahedron Lett. 1991, 32, 7283;
c) MeO-BIPHEP: R. Schmid, J. Foricher, M. Cereghetti, P. Schˆn-
holzer, Helv. Chim. Acta 1991, 74, 370.
[19] a) M. Murata, T. Morimoto, K. Achiwa, Synlett 1991, 827; b) D. J.
Bayston, J. L. Fraser, M. R. Ashton, A. D. Baxter, M. E. C. Polywka,
E. Moses, J. Org. Chem. 1998, 63, 3137; c) T. Benincori, S. Gladiali, S.
¡
Rizzo, F. Sannicolo, J. Org. Chem. 2001, 66, 5940.
[20] Crystallographic data for 3: formula C22H22O3, colorless plate, crystal
dimensions 0.22 Â 0.15 Â 0.10 mm, orthorombic, space group P212121,
a 7.463(5), b 14.702(5), c 16.289(5) ä, V 1787.2(15) A3, Z 4,
1 1.243 gcmÀ3. m 0.082 cmÀ1, KappaCCD diffractometer, MoKa
radiation, l 0.71069 ä, graphite monochromator, T 293.0(10) K,
q max 27.47, À9 ꢀ h ꢀ 9, À19 ꢀ k ꢀ 15, À21 ꢀ l ꢀ 21, 6756 reflections
collected, 4062 independent reflections, 3547 reflections [I > 2s(I)],
fsqd refinement, 230 parameters refined, wR2 0.0967, R1 0.0379,
Flack×s parameter x 0.0(8), GoF 1.017, difference peak/hole
¡
[3] a) BITIANP: T. Benincori, E. Brenna, F. Sannicolo, L. Trimarco, P.
Antognazza, E. Cesarotti, J. Chem. Soc. Chem. Commun. 1995, 685;
¡
b) BICUMP: T. Benincori, E. Brenna, F. Sannicolo, L. Trimarco, P.
Antognazza, E. Cesarotti, F. Demartin, T. Pilati, J. Org. Chem. 1996,
61, 6244; c) 2,2'-bis(diphenylphosphanyl)-3,3'-biindolyl: U. Berens,
J. M. Brown, J. Long, R. Selke, Tetrahedron: Asymmetry 1996, 7, 285;
d) BIFAP: A. E. Sollewijn Gelpke, H. Kooijman, A. L. Spek, H.
Hiemstra, Chem. Eur. J. 1999, 5, 2472; e) BITIOP: T. Benincori, E.
0.051(0.016)/ À 0.068(0.016) eäÀ3
. CCDC-186418 (3) contains the
¡
Cesarotti, O. Piccolo, F. Sannicolo, J. Org. Chem. 2000, 65, 2043;
supplementary crystallographic data (excluding structure factors) for
the structure reported in this paper. These data can be can be obtained
the Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: (44)1223-336033; or deposit@
ccdc.cam.ac.uk).
¡
f) BINP: T. Benincori, O. Piccolo, S. Rizzo, F. Sannicolo, J. Org. Chem.
2000, 65, 8340; g) P-PHOS: C-C. Pai, C-W. Lin, C-C. Lin; C-C. Chen,
A. S. C. Chan, W. T. Wong, J. Am. Chem.Soc. 2000, 122, 11513;
h) BINAPFu: N. G. Andersen, M. Parvez, B. A. Keay, Org. Lett. 2000,
2, 2817.
[4] For a recent review see: M. McCarthy, P. J. Guiry, Tetrahedron 2001,
57, 3809.
Received: January 14, 2002 [F3798]
3330
¹ WILEY-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002
0947-6539/02/0815-3330 $ 20.00+.50/0
Chem. Eur. J. 2002, 8, No. 15