E. Raluy et al. / Tetrahedron: Asymmetry 20 (2009) 1575–1579
1579
121.8 (CH@), 122.6 (CH@), 125.0 (CH@), 125.6 (C), 126.5 (CH@),
127.1 (CH@), 127.2 (CH@), 128.5 (CH@), 129.1 (CH@), 130.8
(CH@), 131.4 (C), 131.8 (C), 133.3 (C). Anal. Calcd (%) for
C32H32NO7P: C, 67.01; H, 5.62; N, 2.44. Found: C, 66.98; H, 5.63;
N, 2.42.
4), 108.7 (CMe2), 109.4 (CMe2), 124.4 (CH@), 124.5 (CH@), 125.3
(C), 127.0 (CH@), 127.2 (CH@), 134.3 (C), 140.9 (C), 146.5 (C),
148.2 (C). Anal. Calcd (%) for C40H60NO7P: C, 68.84; H, 8.67; N,
2.01. Found: C, 68.90; H, 8.65; N, 2.03.
Compound 1g:Yield: 199 mg (35%). 31P NMR (C6D6), d: 152.2 (s,
1P). 1H NMR (C6D6), d: 1.09 (s, 3H, CH3), 1.18 (s, 3H, CH3), 1.25 (s,
3H, CH3), 1.35 (s, 3H, CH3), 3.13 (m, 1H, NH), 4.03 (m, 1H, H-6), 4.06
(m, 1H, H-60), 4.18 (m, 1H, H-3), 4.24 (m, 2H, H-4, H-5), 4.54 (d, 1H,
4.3. General procedure for the Ni-catalyzed enantioselective
1,2-addition of trialkylaluminium reagents to aldehydes
[Ni(acac)2] (0.6 mg, 2.33 lmol, 1 mol %) and ligand (2.33 lmol,
3
3
H-2, J2–1 = 4.0 Hz), 5.29 (d, 1H, H-1, J1–2 = 4.0 Hz), 6.9–7.8 (m,
12H, CH@). 13C NMR (C6D6), d: 25.3 (CH3), 26.2 (CH3), 26.7 (CH3),
27.2 (CH3), 57.8 (d, C-3, JC–P = 7.8 Hz), 67.8 (C-6), 73.9 (C-5), 80.8
(C-4), 86.3 (d, C-2, JC–P = 6.8 Hz), 105.8 (C-1), 109.3 (CMe2), 111.6
(CMe2), 121.9 (CH@), 122.8 (CH@), 125.0 (CH@), 125.4 (C), 126.1
(CH@), 126.7 (CH@), 127.0 (CH@), 128.4 (CH@), 129.6 (CH@),
131.5 (C), 131.9 (C), 133.3 (C). Anal. Calcd (%) for C32H32NO7P: C,
67.01; H, 5.62; N, 2.44. Found: C, 67.09; H, 5.66; N, 2.41.
1 mol %) were stirred in dry THF (2 mL) under argon atmosphere
at ꢁ20 °C for 10 min. Neat aldehyde (0.25 mmol) was then added
and trialkylaluminium (0.5 mmol) was added dropwise after a fur-
ther 10 min. After the desired reaction time, the reaction was
quenched with 2 M HCl (2 mL). Then dodecane (20 lL) was added
and the mixture was extracted with Et2O (10 mL). The organic
layer was dried over MgSO4 and analyzed by GC.
Compound 2c: Yield: 334 mg (48%). 31P NMR (C6D6), d: 149.4 (s,
1P). 1H NMR (C6D6), d: 1.11 (s, 3H, CH3), 1.24 (s, 9H, CH3, t-Bu), 1.26
(s, 9H, CH3, t-Bu), 1.29 (s, 3H, CH3), 1.38 (s, 3H, CH3), 1.47 (s, 3H,
CH3), 1.57 (s, 9H, CH3, t-Bu), 1.63 (s, 9H, CH3, t-Bu), 3.11 (m, 1H,
H-3), 3.22 (m, 1H, NH), 3.56 (m, 1H, H-2), 3.91 (m, 2H, H-60, H-
6), 4.02 (m, 1H, H-4), 4.51 (m, 1H, H-5), 5.45 (d, 1H, H-1,
3J1–2 = 4.0 Hz), 6.8–7.2 (m, 4H, CH@). 13C NMR (C6D6), d: 26.3
(CH3), 26.7 (CH3), 27.0 (CH3), 31.8 (CH3, t-Bu), 31.9 (CH3, t-Bu),
32.0 (CH3, t-Bu), 34.8 (C, t-Bu), 35.0 (C, t-Bu), 35.8 (C, t-Bu), 56.1
(d, C-3, JC–P = 9.2 Hz), 64.4 (C-6), 76.0 (C-5), 79.9 (C-4), 80.5 (C-2),
104,4 (C-1), 109.8 (CMe2), 112.4 (CMe2), 124.4 (CH@), 124.8
(CH@), 125.3 (CH@), 125.5 (C), 125.6 (C), 128.9 (CH@), 138.2 (C),
146.8 (C), 147.3 (C). Anal. Calcd (%) for C40H60NO7P: C, 68.84; H,
8.67; N, 2.01. Found: C, 68.91; H, 8.71; N, 1.99.
4.4. General procedure for the Ni-catalyzed enantioselective
1,2-addition of DABAL-Me3 to aldehydes
[Ni(acac)2] (0.6 mg, 2.33 lmol, 1 mol %) and ligand (2.33 lmol,
1 mol %) were stirred in dry THF (2 mL) under argon atmosphere
at 5 °C for 10 min. Neat aldehyde (0.25 mmol) was then added
and trialkylaluminium (84 mg, 0.325 mmol, 1.3 equiv) was added
after a further 10 min. After the desired reaction time, the reaction
was quenched with 2 M HCl (2 mL). Then dodecane (20 lL) was
added and the mixture was extracted with Et2O (10 mL). The or-
ganic layer was dried over MgSO4 and analyzed by GC.
Acknowledgments
Compound 3d: Yield: 234 mg (38%). 31P NMR (C6D6), d: 154.3 (s,
We thank the Spanish Government (Consolider Ingenio CSD2006–
0003, CTQ2007-62288/BQU, 2008PGIR/07 to O.P. and 2008PGIR/08to
M.D.) and the Catalan Government (2005SGR007777) for financial
support.
1P). 1H NMR (C6D6), d: 0.31 (s, 9H, CH3-Si), 0.42 (s, 9H, CH3-Si), 1.09
(s, 3H, CH3), 1.23 (s, 3H, CH3), 1.60 (s, 3H, CH3), 1.67 (s, 3H, CH3),
2
3.82 (m, 1H, H-2), 3.98 (m, 2H, H-1, H-10), 4.21 (d, 1H, H-60, J6 -
0
6 = 12.0 Hz), 4.51 (m, 1H, H-3), 4.54 (m, 1H, H-4), 5.59 (d, 1H, H-
2
References
0
6, J6–6 = 12.0 Hz), 7.28 (m, 1H, CH@), 7.32 (m, 1H, CH@), 7.54
(m, 2H, CH@). 13C NMR (C6D6), d: 0.5 (CH3-Si), 0.6 (CH3-Si), 26.0
(CH3), 26.5 (CH3), 28.2 (CH3), 28.8 (CH3), 60.9 (C-1), 71.3 (C-6),
72.4 (C-4), 74.7 (C-2), 77.1 (C-3), 104.9 (C-5), 109.6 (CMe2), 112.5
(CMe2), 124.8 (CH@), 124.9 (CH@), 126.2 (C), 127.3 (CH@), 127.9
(CH@), 133.7 (C), 134.9 (C), 140.9 (C), 141.0 (C), 146.8 (C). Anal.
Calcd (%) for C30H44NO7PSi2: C, 58.32; H, 7.18; N, 2.27. Found: C,
58.26; H, 7.21; N, 2.31.
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Compound 4c: Yield: 237 mg (34%). 31P NMR (C6D6), d: 147.1 (s,
1P). 1H NMR (C6D6), d: 1.02 (s, 3H, CH3), 1.06 (s, 3H, CH3), 1.24 (s,
18H, CH3, t-Bu), 1.26 (s, 3H, CH3), 1.34 (s, 3H, CH3), 1.56 (s, 9H, CH3,
t-Bu), 1.59 (s, 9H, CH3, t-Bu), 3.27 (m, 1H, H-6), 3.37 (m, 1H, H-60),
2
2
3.56 (d, 1H, H-1, J1–1 = 9.2 Hz), 3.64 (d, 1H, H-10, J1–1 = 9.2 Hz),
3.72 (m, 1H, H-4), 3.75 (m, 1H, NH), 4.31 (m, 1H, H-3), 4.37 (m, 1H,
H-2), 7.0–7.2 (m, 4H, CH@). 13C NMR (C6D6), d: 24.5 (CH3), 25.7
(CH3), 26.6 (CH3), 30.5 (CH3), 31.7 (CH3, t-Bu), 31.8 (CH3, t-Bu),
32.0 (CH3, t-Bu), 35.0 (C, t-Bu), 35.8 (C, t-Bu), 36.0 (C, t-Bu), 47.5 (C-
6), 61.8 (C-1), 71.1 (C-3), 71.5 (C-4), 72.2 (C-2), 108.2 (CMe2), 109.3
(CMe2), 124.5 (CH@), 125.3 (CH@), 126.2 (CH@), 127.0 (CH@),
137.2 (C), 143.8 (C), 146.6 (C). Anal. Calcd (%) for C40H60NO7P: C,
68.84; H, 8.67; N, 2.01. Found: C, 68.87; H, 8.69; N, 1.98.
0
0
7. Pàmies, O.; Diéguez, M.; Net, G.; Ruiz, A.; Claver, C. Organometallics 2000, 19,
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Compound 5c: Yield: 306 mg (44%). 31P NMR (C6D6), d: 148.5 (s,
1P). 1H NMR (C6D6), d: 1.03 (s, 3H, CH3), 1.08 (s, 3H, CH3), 1.26 (s,
3H, CH3), 1.31 (s, 18H, CH3, t-Bu), 1.42 (s, 3H, CH3), 1.60 (s, 18H,
CH3, t-Bu), 3.17 (m, 2H, H-6, H-60), 3.42 (m, 1H, NH), 3.79 (m, 1H,
H-1), 3.81 (m, 1H, H-5), 4.12 (m, 1H, H-3), 4.40 (m, 1H, H-2),
5.41 (m, 1H, H-4), 7.2–7.6 (m, 4H, CH@). 13C NMR (C6D6), d: 24.7
(CH3), 25.2 (CH3), 26.5 (CH3), 26.6 (CH3), 30.2 (CH3, t-Bu), 31.8
(CH3, t-Bu), 35.6 (C, t-Bu), 35.9 (C, t-Bu), 41.4 (d, C-2, JC–
P = 12.0 Hz), 69.5 (C-5), 71.3 (C-3), 71.5 (C-2), 71.8 (C-1), 96.9 (C-