H. Nakano et al. / Tetrahedron: Asymmetry 16 (2005) 609–614
613
s), 6.37 (1H, d, J = 7.8 Hz), 6.89 (1H, dd, J = 1.6,
4.3 Hz), 7.26–7.32 (10H, m), 7.37 (1H, dd, J = 1.7,
8.1 Hz), 7.71 (1H, dd, J = 4.1, 8.1 Hz). 13C NMR
(CDCl3) d: 20.45, 23.39, 27.25, 29.95, 34.29, 37.85,
41.81, 45.53, 46.74, 64.83, 80.94, 85.62, 127.68, 128.25,
128.38, 128.45, 128.56, 128.71, 131.98, 133.54, 133.91,
134.19, 134.34, 136.35, 136.45, 136.90, 141.06, 141.07,
143.40, 143.64. 31P NMR (CD3COCD3) d: ꢀ17.63 (s).
MS m/z: 488 (M+); HRMS: calcd for C30H33O2PS
(M+): 488.1939, found: 488.1929.
128.49, 128.54, 128.62, 128.78, 128.88, 131.98, 132.12,
132.74, 133.43, 133.72, 133.84, 134.12, 134.43, 136.18,
143.72, 144.67, 17.60. MS m/z: 530 (M+); HRMS: calcd
for C32H35O2PS (M+): 530.2045, found: 530.2072.
4.6. PS–DES-supported ligand 2a
A mixture of 5 (103 mg, 0.21 mmol), chlorodiethylsilyl
polystyrene (PS–DES–Cl, 100 mg, 0.14 mmol), and
imidazole (33 mg, 0.49 mmol) in CH2Cl2 (1 mL) was
stirred at rt for 4 h. The reaction mixture was filtered
and the polymer washed with CHCl3, MeOH, acetone,
and ether. The polymer was dried under reduced pres-
sure to give 2a (130 mg, 77%, 43% conversion,
0.47 mmol/g of ligand in polymer). 31P NMR
(CD3COCD3) d: ꢀ17.64 (s).
4.4. (1R,3R,5R,8S)-11,11-Dimethyl-5-(2-diphenylphosph-
ino-4-triethylsilyloxy-methyl)phenyl-4-oxo-6-thiatricyclo
undecane 6a
To a solution of 5 (65 mg, 0.13 mmol) and imidazole
(18 mg, 0.27 mmol) in CH2Cl2 (5 mL) was added TES–
Cl (0.05 mL, 0.27 mmol) at rt. The reaction mixture
was stirred at rt for 1 h. Then the reaction mixture
was quenched with H2O, extracted twice with ether,
dried over anhydrous MgSO4, and concentrated. The
residue was chromatographed on a column of silica gel
4.7. PS–Et-supported ligand 2b
A mixture of 5 (112 mg, 0.23 mmol), carboxyethylpoly-
styrene (PS–Et–COOH, 100 mg, 0.12 mmol), and diiso-
propylcarbodiimide (DIC, 0.04 mL, 0.23 mmol) in
CH2Cl2 (2 mL) was stirred at rt for 48 h. The reaction
mixture was filtered and the polymer washed with
CHCl3, MeOH, acetone, and ether. The polymer was
dried under reduced pressure to give 2b (124 mg, 79%,
43% conversion, 0.40 mmol/g of ligand in polymer).
31P NMR (CD3COCD3) d: ꢀ18.05 (s).
with AcOEt–hexane = 1:10 to afford 6a (72 mg, 90%);
21
Colorless oil. ½aꢁ ¼ ꢀ84:8 (c 1.05, CHCl3). IR (film)
D
cmꢀ1 = 759, 1216, 3019. 1H NMR (CDCl3) d: 0.48
(6H, q, J = 8.0 Hz), 0.84 (9H, t, J = 7.9 Hz), 0.91 (3H,
s), 0.94–1.05 (2H, m), 1.43–1.56 (4H, m), 1.59–1.69
(3H, m), 1.84–1.89 (1H, m), 2.70 (1H, d, J = 14.2 Hz),
3.19 (1H, d, J = 14.2 Hz), 3.59 (1H, dd, J = 2.9,
7.8 Hz), 4.56 (2H, s), 6.38 (1H, d, J = 7.7 Hz), 6.94
(1H, d, J = 3.0 Hz), 7.26–7.32 (11H, m), 7.67 (1H, dd,
J = 4.3, 7.9 Hz). 13C NMR (CDCl3) d: 4.42, 5.39, 5.81,
6.59, 6.74, 7.29, 20.47, 23.41, 27.28, 29.98, 34.33,
37.88, 41.84, 45.58, 46.78, 65.00, 81.00, 85.65, 127.28,
127.44, 127.75, 128.36, 128.43, 128.51, 128.64, 131.35,
132.05, 134.56, 133.74, 133.86, 134.19, 136.43, 136.78,
141.27, 142.86, 143.63. MS m/z: 602 (M+); HRMS: calcd
for C36H47O2PSSi (M+): 602.2803, found: 602.2789.
4.8. TentaGel-supported ligand 2c
A mixture of 5 (30 mg, 0.06 mmol), TentaGel MB–
COOH (100 mg, 0.04 mmol), and DIC (0.01 mL,
0.8 mmol) in CH2Cl2 (2 mL) was stirred at rt for 48 h.
The reaction mixture was filtered and the polymer
washed with CHCl3, MeOH, acetone, and ether. The
polymer was dried under reduced pressure to give 2c
(107 mg, 92%, 36% conversion, 0.13 mmol/g of ligand
in polymer). 31P NMR (CD3COCD3) d: ꢀ17.93 (s).
4.5. (1R,3R,5R,8S)-5-(4-Acetoxymethyl-2-diphenyl-
phosphino)phenyl-11,11-dimethyl-4-oxo-6-thiatricyclo
undecane 6b
4.9. General procedure for the Pd-catalyzed allylic
alkylation using polymer-supported ligand
To a solution of 5 (50 mg, 0.10 mmol) and Et3N
(0.03 mL, 0.20 mmol) in CH2Cl2 (5 mL) was added
Ac2O (0.01 mL, 0.15 mmol) at rt. The reaction mixture
was stirred for 5 h at rt. The mixture was quenched with
H2O and extracted twice with CHCl3. The combined or-
ganic layers were washed with brine, dried over anhy-
drous MgSO4, and concentrated. The residue was
chromatographed on a column of silica gel with
A mixture of polymer-supported ligand (0.01 mmol,
5 mol %),
[PdCl(g3-C3H5)]2
(2 mg,
0.005 mmol,
2.5 mol %), 1,3-diphenyl-2-propenyl acetate 7 (50 mg,
0.2 mmol), and KOAc (0.4 mg, 0.004 mmol, 2 mol %)
in CH2Cl2 (1 mL) was stirred for 1 h at rt under argon.
To this mixture at the desired reaction temperature was
added dimethyl malonate (0.07 mL, 0.59 mmol) and
N,O-bis(trimethylsilyl)acetamide (0.15 mL, 0.59 mmol).
After 24 h, the reaction mixture was quenched with sat-
urated NH4Cl solution and filtered. The filtrate was ex-
tracted twice with ether. The combined organic layers
were washed with brine, dried over anhydrous MgSO4,
and concentrated. The residue was purified by prepara-
tive TLC (hexane–AcOEt = 2:1) to afford 8.
AcOEt–hexane = 1:10 to afford 6b (45 mg, 83%); Color-
20
less oil. ½aꢁ ¼ ꢀ73:0 (c 1.00, CHCl3). IR (film)
D
1
cmꢀ1 = 756, 1216, 1249, 1733, 3021. H NMR (CDCl3)
d: 0.86–0.88 (1H, m), 0.92 (3H, s), 0.95–1.06 (1H, m),
1.42 (1H, s), 1.45 (3H, s), 1.59–1.72 (3H, m), 1.83–1.89
(1H, m), 1.97 (3H, s), 2.71 (1H, d, J = 14.2 Hz), 3.18
(1H, d, J = 14.2 Hz), 3.55 (1H, dd, J = 3.0, 8.0 Hz),
4.93 (2H, s), 6.34 (1H, d, J = 7.3 Hz), 6.84 (1H, dd,
J = 1.5, 4.3 Hz), 7.27–7.37 (10H, m), 7.47–7.57 (1H,
m), 7.71 (1H, dd, J = 4.2, 8.0 Hz). 13C NMR (CDCl3)
d: 20.42, 23.36, 27.23, 29.69, 29.95, 34.29, 37.23, 41.83,
45.54, 46.74, 65.59, 81.35, 85.38, 127.67, 128.39,
4.10. General procedure for the Pd-catalyzed allylic
amination using polymer-supported ligand
A mixture of polymer-supported ligand (0.01 mmol,
[PdCl(g3-C3H5)]2
5 mol %),
(2 mg,
0.005 mmol,