E. Raluy et al. / Tetrahedron: Asymmetry 20 (2009) 1930–1935
1935
CH
H, CH
m, 1H, H-4), 3.61 (m, 1H, H-3), 3.88 (m, 1H, H-2), 4.05 (m, 1H, H-
3
), 2.07 (s, 3H, CH
3
), 2.10 (s, 3H, CH
3
), 2.11 (s, 3H, CH
3
), 2.29 (s,
Yamamoto, H., Eds.; Springer: New York, 2000; p 1105; (d) Sibi, M. P.; Manyem,
S. Tetrahedron 2000, 56, 8033; (e) Krause, N.; Hoffmann-Röder, A. Synthesis
3
(
3
), 2.30 (s, 6H, CH
3
), 2.33 (s, 3H, CH
3
), 3.35 (m, 1H, NH), 3.54
2001, 171; (f) Alexakis, A. In Methodologies in Asymmetric Catalysis; American
Chemical Society: Washington DC, 2004. Chapter 4; (g) Krause, N. Modern
Organocopper Chemistry; Wiley-VCH: Weinheim, 2002; (h) Alexakis, A.;
Benhaim, C. Eur. J. Org. Chem. 2002, 3211; (i) Woodward, S. Chem. Soc. Rev.
0
3
5
8
1
), 4.31 (m, 1H, H-5 ), 5.43 (d, 1H, H-1, J1–2 = 3.6 Hz), 6.7–7.2 (m,
1
3
H, CH@). C NMR (C
7.5 (CH ), 21.1 (CH
), 53.4 (d, C-3, JC–P = 14.4 Hz), 62.6 (d, C-5, JC–P = 5.3 Hz), 80.8
C-2), 81.0 (C-4), 104.8 (C-1), 112.3 (CMe ), 126.0 (CH@), 128.7
CH@), 128.8 (CH@), 129.6 (CH@), 130.2 (C), 130.6 (C), 130.7 (C),
6
D
6
3
), d: 17.1 (CH ), 17.2 (CH
3
), 17.3 (CH
3
),
2000, 29, 393; (j) Alexakis, A.; Bäckvall, J. E.; Krause, N.; Pàmies, O.; Diéguez, M.
3
3
), 21.2 (CH ), 21.3 (CH
3
3 3
), 26.8 (CH ), 27.1
Chem. Rev. 2008, 108, 2796; (k) Haratyunyan, S. R.; den Hartog, T.; Geurts, K.;
Minnaard, A. J.; Feringa, B. L. Chem. Rev. 2008, 108, 2824.
(
(
(
CH
3
2
.
See also for instance: (a) Feringa, B. L. Acc. Chem. Res. 2000, 33, 346; (b) Escher, I.
H.; Pfaltz, A. Tetrahedron 2000, 56, 2879; (c) Hu, X.; Chen, H.; Zhang, X. Angew.
Chem., Int. Ed. 1999, 38, 3518; (d) Yan, M.; Zhou, Z.-Y.; Chan, A. S. C. Chem.
Commun. 2000, 115; (e) Borner, C.; Dennis, M. R.; Sinn, E.; Woodward, S. Eur. J.
Org. Chem. 2001, 2435; (f) Rimkus, A.; Sewald, N. Synthesis 2004, 135; (g) Hua,
Z.; Vassar, V. C.; Choi, H.; Ojima, I. Proc. Natl. Acad. Sci. 2004, 101, 5411; (h)
Watanabe, T.; Knoepfel, T. F.; Carreira, E. M. Org. Lett. 2003, 5, 4557; (i) Li, K.;
Alexakis, A. Angew. Chem., Int. Ed. 2006, 45, 7600; (j) Fillion, E.; Wilsily, A. J. Am.
Chem. Soc. 2006, 128, 2774; (k) Pineschi, M.; Del Moro, F.; Bussolo, V. D.;
Macchia, F. Adv. Synth. Catal. 2006, 348, 301; (l) Wan, H.; Hu, Y.; Liang, Y.; Gao,
S.; Wang, J.; Zheng, Z.; Hu, X. J. Org. Chem. 2003, 68, 8277.
2
1
1
31.4 (CH@), 131.6 (CH@), 131.8 (CH@), 131.9 (CH@), 132.2 (C),
32.4 (C), 133.9 (C), 134.0 (C), 146.9 (C), 147.2 (C), 147.5 (C). Anal.
Calcd for C40
H, 6.24; N, 1.94.
L4e: Yield: 0.29 g, 39%. 31P NMR (C
NMR (C ), d: 1.04 (s, 3H, CH ), 1.20 (s, 3H, CH
.36 (m, 1H, H-4), 3.58 (m, 5H, NH, CH ), 3.78 (m, 1H, H-2), 3.92 (m,
H, H-5), 4.21 (m, 1H, H-5 ), 5.01 (m, 4H, CH @), 5.42 (d, 1H, H-1,
H45NO
8
2
P : C, 65.84; H, 6.22; N, 1.92. Found: C, 65.86;
1
6
D
6
), d: 142.3 (s), 145.8 (s). H
6
D
6
3
3
), 3.24 (m, 1H, H-3),
3
1
2
3. See for instance: (a) Takemoto, Y.; Kuraoka, S.; Humaue, N.; Aoe, K.; Hiramatsu,
H.; Iwata, C. Tetrahedron 1996, 52, 14177; (b) Diéguez, M.; Deerenberg, S.;
Pàmies, O.; Claver, C.; van Leeuwen, P. W. N. M.; Kamer, P. Tetrahedron:
Asymmetry 2000, 11, 3161; (c) Chataigner, I.; Gennari, C.; Ongeri, S.; Piarulli, U.;
Ceccarelli, S. Chem. Eur. J. 2001, 7, 2628; (d) Liang, L.; Chan, A. S. C. Tetrahedron:
Asymmetry 2002, 13, 1393; (e) Fraser, P. K.; Woodward, S. Chem. Eur. J. 2003, 9,
0
2
3
13
J
1–2 = 3.6 Hz), 5.94 (m, 2H, CH@), 6.8–7.2 (m, 12H, CH@).
), d: 26.7 (CH ), 27.0 (CH ), 35.1 (CH ), 35.2 (CH ), 35.3
), 35.5 (CH ), 53.6 (d, C-3, JC–P = 12 Hz), 63.3 (d, C-5, JC–P
.2 Hz), 80.6 (C-2 and C-4), 104.7 (C-1), 112.3 (CMe ), 116.7
CH @), 116.8 (CH @), 125.2 (CH@), 125.4 (CH@), 128.9 (CH@)
C
NMR (C
CH
6
D
6
3
3
2
2
(
2
2
=
776; (f) Su, L.; Li, X.; Chan, W. L.; Jia, X.; Chan, A. S. C. Tetrahedron: Asymmetry
6
(
2
2003, 14, 1865; (g) Eilitz, U.; Leßmann, F.; Seidelmann, O.; Wendisch, V.
2
2
Tetrahedron: Asymmetry 2003, 14, 3095; (h) d’Augustin, M.; Palais, L.; Alexakis,
A. Angew. Chem., Int. Ed. 2005, 44, 1376; (i) Alexakis, A.; Albrow, V.; Biswas, K.;
d’Augustin, M.; Prieto, O.; Woodward, S. Chem. Commun. 2005, 2843; (j)
Albrow, V. E.; Blake, A. J.; Fryatt, R.; Wilson, C.; Woodward, S. Eur. J. Org. Chem.
1
1
1
C
29.6 (CH@), 129.7 (CH@), 130.1 (CH@), 132.6 (C), 132.8 (C),
33.3 (C), 136.8 (CH@ allyl), 137.1 (CH@ allyl), 137.2 (CH@ allyl),
37.3 (CH@ allyl), 148.8 (C), 149.2 (C), 149.3 (C). Anal. Calcd for
2006, 2549; (k) d’Augustin, M.; Alexakis, A. Chem. Eur. J. 2007, 13, 9647.
44
H45NO P
8 2
: C, 67.95; H, 5.83; N, 1.80. Found: C, 67.94; H, 5.82;
4. Ligands L1–L4a–c,f,g have been successfully applied in the Pd-catalyzed allylic
substitution reaction and in the Rh-catalyzed hydrogenation. See: (a) Diéguez,
M.; Ruiz, A.; Claver, C. Chem. Commun. 2001, 2702; (b) Diéguez, M.; Ruiz, A.;
Claver, C. Tetrahedron: Asymmetry 2001, 12, 2827; (c) Raluy, E.; Claver, C.;
Pàmies, O.; Diéguez, M. Org. Lett. 2007, 9, 49; (d) Raluy, E.; Pàmies, O.; Diéguez,
M. Adv. Synth. Catal. 2009, 351, 1648.
N, 1.84.
4
.3. Typical procedure for the catalytic conjugate addition of
alkylating reagents to enones
5.
Ligands 5a–g have been successfully applied in the Pd-catalyzed allylic
substitution reaction. See: Raluy, E.; Diéguez, M.; Pàmies, O. J. Org. Chem.
2007, 72, 2842.
In a typical procedure, a solution of copper-catalyst precursor
(
8.3
l
mol) and furanoside ligand (8.3
l
mol) in the appropriate sol-
6. See for instance: (a) Feringa, B. L. Acc. Chem. Res. 2000, 33, 346; (b) Diéguez,
M.; Pàmies, O.; Claver, C. Chem. Rev. 2004, 104, 3189; (c) Diéguez, M.;
Pàmies, O.; Ruiz, A.; Díaz, Y.; Castillón, S.; Claver, C. Coord. Chem. Rev. 2004,
vent (2 mL) was stirred for 30 min at room temperature. After cool-
ing to the desired temperature, the alkylating reagent (0.62 mmol)
was added. A solution of the desired enone (0.415 mmol) and unde-
cane as a GC internal standard (0.25 mL) in dichloromethane
2
48, 2165; (d) Diéguez, M.; Ruiz, A.; Claver, C. Dalton Trans. 2003, 2957; (e)
Pàmies, O.; Diéguez, M.; Ruiz, A.; Claver, C. Chem. Today 2004, 12; (f)
Diéguez, M.; Pàmies, O.; Ruiz, A.; Claver, C. In Methodologies in Asymmetric
Catalysis; Malhotra, S. V., Ed.; American Chemical Society: Washington DC,
(
0.5 mL), was then added at the corresponding reaction tempera-
2
004; (g) Diéguez, M.; Pàmies, O.; Claver, C. Tetrahedron: Asymmetry 2004,
15, 2113; (h) Diéguez, M.; Claver, C.; Pàmies, O. Eur. J. Org. Chem. 2007, 4621;
i) Minnaard, A. J.; Feringa, B. L.; Lefort, L.; de Vries, J. G. Acc. Chem. Res.
007, 40, 1267; (j) Börner, A. Phosphorous Ligands in Asymmetric Catalysis;
ture. The reaction was monitored by GC. The reaction was quenched
with HCl (2 M) and filtered twice through flash silica. Conversion,
chemoselectivity, and enantioselectivity were obtained by GC.
(
2
3
i
Wiley-VCH: Weinheim, 2008.
7
.
.
Pàmies, O.; Diéguez, M.; Net, G.; Ruiz, A.; Claver, C. Organometallics 2000, 19,
1
488.
Alexakis, A.; Benhaim, C.; Rosset, S.; Humam, M. J. Am. Chem. Soc. 2002, 124,
262.
Acknowledgments
8
5
WewouldliketothanktheSpanish Government(ConsoliderInge-
nio CSD2006-0003, CTQ2007-62288/BQU, 2008PGIR/07 to O.P. and
9. These reaction conditions were also found to be optimal in the Cu-catalyzed
conjugate addition of S1 using related furanoside diphosphite ligands, see: (a)
Pàmies, O.; Net, G.; Ruiz, A.; Claver, C. Tetrahedron: Asymmetry 1999, 10, 2007;
2
008PGIR/08 to M.D.), the Catalan Government (2005SGR007777),
the Swiss National Research Foundation (Grant No. 200020-
13332) and COST action D40 (SER Contract No. C07.0097) for their
(
b) Pàmies, O.; Diéguez, M.; Net, G.; Ruiz, A.; Claver, C. Tetrahedron: Asymmetry
2000, 11, 4377; (c) Diéguez, M.; Ruiz, A.; Claver, C. Tetrahedron: Asymmetry
2001, 12, 2895.
1
1
0. (a) Alexakis, A.; Benhaïm, C.; Fournioux, X.; van der Hwuvel, A.; Levéque, J. M.;
March, S.; Rosset, S. Synlett 1999, 1811; (b) Bennett, S. M. W.; Brown, S. M.;
Muxworthy, J. P.; Woodward, S. Tetrahedron Lett. 1999, 40, 1767; (c) Bennett, S.
M. W.; Brown, S. M.; Cunnigham, A.; Dennis, M. R.; Muxworthy, J. P.; Oakley, M.
A.; Woodward, S. Tetrahedron 2000, 56, 2847; (d) De Roma, A.; Ruffo, F.;
Woodward, S. Chem. Commun. 2008, 5384.
financial support.
References
1
.
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1
1
1
1. Berner, O. M.; Tedeschi, L.; Enders, D. Eur. J. Org. Chem. 2002, 1877.
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3. Raluy, E.; Diéguez, M.; Pàmies, O. Tetrahedron Lett. 2009, 50, 4495.