838
S. Alegre et al. / Tetrahedron: Asymmetry 22 (2011) 834–839
3J1-2 = 3.6 Hz), 7.29 (m, 2H, CH@), 7.56 (m, 2H, CH@). 13C NMR
(C6D6), d: 21.0 (d, CH3, JC-P = 9.6 Hz), 25.2 (CH3), 26.3 (CH3), 26.4
(CH2, iPr), 69.4 (C-6), 73.5 (C-5), 79.2 (C-2), 82.0 (d, C-4, JC-
P = 16.7 Hz), 89.5 (C-3), 105.1 (C-1), 110.7 (CMe2), 113.4 (CMe2),
122.6 (CH@), 123.8 (CH@), 125.2 (CH@), 126.0 (CH@), 126.7
(CH@), 126.8 (CH@), 127.7 (CH@), 127.8 (CH@), 128.9 (CH@),
129.0 (CH@), 129.6 (CH@), 130.7 (CH@), 131.9 (C), 132.2 (C),
133.7 (C), 134.0 (C), 149.6 (C), 149.7 (C). Anal. Calcd for
t
t
t
(CH3), 26.8 (CH3), 31.0 (CH3, Bu), 31.2 (CH3, Bu), 31.3 (CH3, Bu),
t
t
t
t
31.5 (CH3, Bu), 34.2 (C, Bu), 34.3 (C, Bu), 35.2 (C, Bu), 35.5 (C,
tBu), 65.7 (C-6), 73.6 (C-5), 80.6 (d, C-4, JC-P = 5.3 Hz), 82.7 (C-2),
83.8 (C-3), 103.6 (C-1), 108.6 (CMe2), 112.9 (CMe2), 123.7 (CH@),
124.0 (CH@), 126.5 (CH@), 126.9 (CH@), 133.4 (C), 134.0 (C),
140.1 (C), 140.5 (C), 146.0 (C), 146.2 (C), 146.4 (C). Anal. Calcd for
C35H37O8P: C, 68.17; H, 6.05. Found: C, 68.21; H, 6.08.
C41H61O8P: C, 69.08; H, 8.62. Found: C, 69.05; H, 8.60.
4.2.9. Compound 7b
Yield: 351 mg (53%). 31P NMR (C6D6), d: 147.5 (s, 1P). 1H NMR
(C6D6), d: 1.05 (s, 3H, CH3), 1.37 (s, 3H, CH3), 1.58 (s, 3H, CH3),
1.72 (s, 3H, CH3), 2.40 (m, 1H, CH2-Ph), 3.35 (m, 1H, CH2-Ph),
4.2.5. Compound 4b
Yield: 441 mg (75%). 31P NMR (C6D6), d: 150.9 (s, 1P). 1H NMR
(C6D6), d: 1.20 (s, 3H, CH3), 1.24 (s, 3H, CH3), 1.28 (s, 3H, CH3),
1.29 (s, 3H, CH3), 1.56 (s, 3H, CH3), 3.99 (m, 4H, H-60, H-6, H-5
2
3
3.78 (dd, 1H, H-60, J6-6 = 8.8 Hz, J6-5 = 6.8 Hz), 4.06 (m, 1H, H-6),
0
3
4.21 (m, 1H, H-5), 4.39 (d, 1H, H-2, J2-1 = 3.6 Hz), 5.03 (dd, 1H,
3
and H-2), 4.57 (dd, 1H, H-4, J4-5 = 3.2 Hz, J4-P = 8.0 Hz), 5.38 (d,
3
3
H-4, J4-5 = 5.6 Hz, J4-P = 8.0 Hz), 5.62 (d, 1H, H-1, J1-2 = 3.6 Hz),
6.82–7.76 (m, 17H, CH@). 13C NMR (C6D6), d: 25.0 (CH3), 25.4
(CH3), 26.0 (CH3), 26.4 (CH3), 38.2 (CH2-Ph), 68.5 (C-6), 72.8 (C-
5), 78.2 (d, C-4, JC-P = 7.5 Hz), 80.2 (C-2), 85.9 (C-3), 103.3 (C-1),
109.9 (CMe2), 113.1 (CMe2), 121.8 (CH@), 122.7 (CH@), 123.5 (C),
124.6 (CH@), 125.3 (CH@), 126.2 (CH@), 126.3 (CH@), 127.0
(CH@), 127.1 (CH@), 128.1 (CH@), 128.9 (CH@), 129.6 (C), 130.1
(C), 130.9 (CH@), 131.1 (C), 131.6 (C), 132.8 (C), 133.2 (C), 134.9
(C), 148.6 (C), 148.8 (C). Anal. Calcd for C39H37O8P: C, 70.47; H,
5.61. Found: C, 70.45; H, 5.63.
3
1H, H-1, J1-2 = 4.0 Hz), 6.91–7.81 (m, 12H, CH@). 13C NMR
(C6D6), d: 20.5 (d, CH3, JC-P = 5.3 Hz), 25.3 (CH3), 26.4 (CH3), 26.6
(CH3), 26.7 (CH3), 67.6 (C-6), 73.6, 79.5 (d, C-4, JC-P = 9.9 Hz), 83.4
(d, C-3, JC-P = 5.3 Hz), 84.3, 103.7 (C-1), 109.6 (CMe2), 113.1
(CMe2), 121.9 (CH@), 122.8 (CH@), 124.6 (CH@), 126.0 (CH@),
126.2 (CH@), 127.4 (CH@), 128.1 (CH@), 128.3 (CH@), 129.1
(CH@), 130.1 (CH@), 131.2 (C), 131.6 (C), 132.9 (C), 133.2 (C),
148.4 (C), 148.6 (C). Anal. Calcd for C33H33O8P: C, 67.34; H, 5.65.
Found: C, 67.41; H, 5.68.
4.2.6. Compound 4c
Yield: 322 mg (55%). 31P NMR (C6D6), d: 149.1 (s, 1P). 1H NMR
(C6D6), d: 1.08 (s, 3H, CH3), 1.20 (s, 3H, CH3), 1.29 (s, 3H, CH3),
4.2.10. Compound 8b
Yield: 441 mg (68%). 31P NMR (C6D6), d: 146.9 (s, 1P). 1H NMR
(C6D6), d: 1.15 (s, 3H, CH3), 1.24 (s, 3H, CH3), 1.54 (s, 3H, CH3),
3
1.37 (s, 3H, CH3), 2.67 (s, 3H, CH3), 3.87 (d, 1H, H-2, J2-
3
1 = 3.6 Hz), 3.99 (m, 3H, H-60, H-6 and H-5), 4.65 (dd, 1H, H-4, J4-
2
3
1.69 (s, 3H, CH3), 3.43 (dd, 1H, H-60, J6-6 = 7.6 Hz, J6-5 = 5.6 Hz),
3.81 (m, 1H, H-5), 3.85 (m, 1H, H-6), 4.55 (d, 1H, H-2, J2-
1 = 3.6 Hz), 5.21 (t, 1H, H-4, J = 7.2 Hz), 5.75 (d, 1H, H-1, J1-
0
3
3
5 = 4.0 Hz, J4-P = 7.2 Hz), 5.29 (d, 1H, H-1, J1-2 = 3.6 Hz), 6.91–7.81
(m, 12H, CH@). 13C NMR (C6D6), d: 20.5 (d, CH3, JC-P = 3.8 Hz),
26.1 (CH3), 27.0 (CH3), 27.2 (CH3), 27.3 (CH3), 68.5 (C-6), 74.3,
80.2 (d, C-4, JC-P = 12.2 Hz), 84.0 (d, C-3, JC-P = 2.2 Hz), 84.9 (C-2),
104.2 (C-1), 110.5 (CMe2), 113.5 (CMe2), 123.7 (CH@), 125.4
(CH@), 125.5 (CH@), 126.9 (CH@), 127.6 (CH@), 127.9 (CH@),
128.1 (CH@), 128.9 (CH@), 129.0 (CH@), 129.1 (CH@), 129.6
(CH@), 129.9 (CH@), 130.7 (C), 132.0 (C), 132.3 (C), 133.6 (C),
133.9 (C), 149.3 (C), 149.6 (C). Anal. Calcd for C33H33O8P: C,
67.34; H, 5.65. Found: C, 67.39; H, 5.69.
3
2 = 3.6 Hz), 6.89–7.71 (m, 17H, CH@). 13C NMR (C6D6), d: 25.1
(CH3), 26.4 (CH3), 26.5 (CH3), 26.6 (CH3), 66.4 (C-6), 73.5 (C-5),
80.1 (d, C-4, JC-P = 16.9 Hz), 84.5 (C-2), 87.8 (C-3), 104.9 (C-1),
109.2 (CMe2), 113.3 (CMe2), 121.9 (CH@), 122.5 (CH@), 123.6 (C),
124.5 (CH@), 124.7 (CH@), 125.3 (CH@), 126.2 (CH@), 126.3
(CH@), 127.0 (CH@), 127.2 (CH@), 128.2 (CH@), 128.3 (CH@),
128.9 (CH@), 129.3 (C), 130.3 (C), 131.2 (CH@), 131.6 (C), 132.8
(C), 133.5 (C), 137.5 (C), 138.2 (C), 148.5 (C), 148.8 (C). Anal. Calcd
for C38H35O8P: C, 70.15; H, 5.42. Found: C, 70.11; H, 5.38.
4.2.7. Compound 5b
Yield: 458 mg (76%). 31P NMR (C6D6), d: 148.7 (s, 1P). 1H NMR
(C6D6), d: 0.73 (m, 3H, CH3, Et), 1.19 (m, 1H, CH2, Et), 1.22 (s, 3H,
CH3), 1.31 (s, 3H, CH3), 1.51 (s, 3H, CH3), 1.63 (s, 3H, CH3), 1.89
(m, 1H, CH2, Et), 4.02 (m, 2H, H-60 and H-6), 4.08 (m, 1H, H-5),
4.3. General procedure for the Ni-catalyzed enantioselective 1,2-
addition of trialkylaluminum reagents to aldehydes
At first, [Ni(acac)2] (2.4 mg, 9.32
lmol, 1 mol %) and ligand
3
3
4.28 (d, 1H, H-2, J2-1 = 3.6 Hz), 4.79 (dd, 1H, H-4, J4-5 = 5.2 Hz,
(9.32 mol, 1 mol %) were stirred in dry THF (8 mL) under an argon
l
3
J4-P = 8.4 Hz), 5.39 (d, 1H, H-1, J1-2 = 4.0 Hz), 6.92–7.79 (m, 12H,
atmosphere at ꢂ20 °C for 10 min. Neat aldehyde (1 mmol) was
then added and trialkylaluminum (2 mmol) was added dropwise
over 10 min. After the desired reaction time, the reaction was
quenched with 2 M HCl (8 mL). The mixture was extracted with
Et2O (10 mL). The organic layer was dried over MgSO4 and ana-
lyzed by GC.5a
CH@). 13C NMR (C6D6), d: 7.1 (CH3, Et), 21.0 (b, CH2, Et), 24.9
(CH3), 25.1 (CH3), 26.5 (CH3), 26.6 (CH3), 68.1 (C-6), 73.0 (C-5),
79.8 (d, C-4, JC-P = 12.4 Hz), 80.1 (C-2), 86.2 (C-3), 103.7 (C-1),
109.6 (CMe2), 112.9 (CMe2), 121.9 (CH@), 123.0 (CH@), 124.5
(CH@), 126.0 (CH@), 126.1 (CH@), 127.0 (CH@), 127.1 (CH@),
128.1 (CH@), 128.3 (CH@), 128.9 (CH@), 130.0 (CH@), 131.2 (C),
131.5 (C), 132.9 (C), 133.2 (C), 148.7 (C), 148.8 (C). Anal. Calcd
for C34H35O8P: C, 67.77; H, 5.85. Found: C, 67.74; H, 5.86.
4.4. General procedure for the Ni-catalyzed enantioselective 1,2-
addition of DABAL-Me3 to aldehydes
4.2.8. Compound 6b
Yield: 336 mg (55%). 31P NMR (C6D6), d: 147.6 (s, 1P). 1H NMR
At first, [Ni(acac)2] (2.4 mg, 9.32
lmol, 1 mol %) and ligand
i
3
(9.32 mol, 1 mol %) were stirred in dry THF (8 mL) under an argon
l
(C6D6), d: 0.62 (d, 3H, CH3, Pr, JH-H = 7.2 Hz), 0.76 (d, 3H, CH3,
3
iPr, JH-H = 7.2 Hz), 1.24 (s, 3H, CH3), 1.34 (s, 3H, CH3), 1.58 (s, 3H,
atmosphere at 5 °C for 10 min. Neat aldehyde (1 mmol) was then
added and DABAL-Me3 (336 mg, 1.3 mmol, 1.3 equiv) was added
over 10 min. After the desired reaction time, the reaction was
quenched with 2 M HCl (8 mL). The mixture was extracted with
Et2O (10 mL). The organic layer was dried over MgSO4 and ana-
lyzed by GC.5a
i
CH3), 1.68 (s, 3H, CH3), 2.34 (m, 1H, CH, Pr), 4.07 (m, 2H, H-60
3
and H-6), 4.25 (m, 1H, H-5), 4.30 (d, 1H, H-2, J2-1 = 4.0 Hz), 4.93
3
3
(dd, 1H, H-4, J4-5 = 8.0 Hz, J4-P = 9.2 Hz), 5.47 (d, 1H, H-1, J1-
2 = 4.0 Hz), 6.92–7.80 (m, 12H, CH@). 13C NMR (C6D6), d: 17.6
(CH3, Pr), 18.4 (CH3, Pr), 25.9 (CH3), 27.2 (CH3), 27.3 (CH3), 31.4
i
i