624 J . Org. Chem., Vol. 66, No. 2, 2001
Notes
Ta ble 3. Asym m etr ic P d -Ca ta lyzed Am in a tion of Aceta te 8 Usin g Ben zyla m in e or P ota ssiu m P h th a lim id e
nucleophile
(equiv to 8)
entry
ligand
nucleophile
temp (°C)
time (h)
yieldc (%)
eed (%)
confige
1a
2
3
4
5
6
7
8
9
3
3
3
3
3
3
5
5
5
3
3
3
3
5
5
13
13
13
13
13
13
13
13
13
15
15
15
15
15
15
1
10
1
10
1
10
1
10
10
3
rt
rt
0
3
1
3
30
98
16
67
12
15
8
30
27
100
86
74
31
100
98
77
76
81
82
85
86
46
52
60
73
88
90
89
50
51
S
S
S
S
S
S
R
R
R
S
S
S
S
R
R
0
3
-30
-30
0
24
24
3
0
3
-30
50
rt
0
-30
rt
24
18
24
48
48
24
48
10b
11
12
13
14
15
3
3
3
3
3
0
a
Molar ratio for entries 1-9: [PdCl(η3-C3H5)]2 (0.01 equiv), benzylamine [entries 1, 3, 5, 7: (1 equiv), entries 2, 4, 6, 8, 9: (10 equiv),
8 (1 equiv), ligands 3, 5 (0.02 equiv). Molar ratio for entries 10-15: [PdCl(η3-C3H5)]2 (0.025 equiv), potassium phthalimide (3 equiv), 8
b
(1 equiv), ligands 3, 5 (0.05 equiv). c Isolated yields. Determined by HPLC analysis using a DAICEL Chiralcel OD-H column. e R or S
d
configurations based on the specific rotation with literature data.3m,9a,d
a reduced pressure, and the residue was purified by preparative
TLC (hexane:ether ) 6:1) to give a pure 3 (230 mg) in 92% yield.
(d, J ) 8.2 Hz, 1H), 3.39 (ddd, J ) 10.2, 10.1, 4.0 Hz, 1H), 1.82
(m, 1H), 1.66-1.79 (m, 2H), 1.50 (m, 1H), 1.40 (m, 1H), 1.36 (s,
3H), 1.19 (s, 3H), 1.05 (br q, 1H), 0.87 (d, J ) 6.6 Hz, 3H), 0.86
(m, 2H). 13C NMR (CDCl3) δ: 143.44, 143.10, 137.08, 136.28,
136.14, 134.23, 133.94, 133.73, 133.44, 133.39, 129.39, 128.59,
128.37, 128.35, 128.32, 128.25, 128.23, 127.56, 78.68, 78.21,
77.83, 50.59, 44.34, 41.72, 34.82, 31.51, 24.48, 22.48, 22.17. Anal.
Calcd for C29H33OPS: C, 75.62; H, 7.22. Found: C, 75.45; H,
6.97. MS m/z: 460 (M+).
mp 52-54 °C, [R]23 ) -96.1 (c 1.51, CHCl3). IR (film) cm-1
:
D
746, 719, 702. 1H NMR (CDCl3) δ: 7.71 (m, 1H), 7.35-7.46 (m,
12H), 6.92 (m, 1H), 6.39 (d, J ) 7.6 Hz, 1H), 3.59 (dd, J ) 7.0,
3.0 Hz, 1H), 3.19 (d, J ) 14.2 Hz, 1H), 2.70 (d, J ) 14.2 Hz, 1H),
1.88 (m, 1H), 1.59-1.72 (m, 3H) 1.47 (m, 1H), 1.46 (s, 3H), 0.88-
1.10 (m, 2H), 0.92 (s, 3H). 13C NMR (CDCl3) δ: 137.2, 137.1,
136.7, 134.0, 133.9, 133.8, 133.8, 133.7, 133.5, 129.6, 128.6, 128.6,
128.5, 128.5, 128.4, 128.4, 128.3, 127.3, 85.6, 81.3, 81.0, 46.8,
Typ ica l P r oced u r e of P d -Ca ta lyzed Asym m etr ic Allyl-
a tion of r a c-1,3-Dip h en yl-2-p r op en yl Aceta te (8) w ith
Dim eth yl Ma lon a te. A mixture of the ligand 3 (3.67 mg, 0.008
mmol) and [PdCl(η3-C3H5)]2 (1.46 mg, 0.004 mmol) in dry
dichloromethane (1 mL) was stirred at room temperature for 1
h, and the resulting yellow solution was added to a mixture of
acetate 8 (100 mg, 0.40 mmol) and potassium acetate (0.8 mg,
0.008 mmol) in dry dichloromethane (1 mL) followed by the
addition of dimethyl malonate (160 mg, 1.20 mmol) and BSA
(240 mg, 1.20 mmol). The reaction was carried out an ambient
temperature. The reaction mixture was diluted with ether and
quenched with sat. NH4Cl. The organic layer was washed with
brine and dried over MgSO4. The solvent was evaporated under
a reduced pressure, and the residue was purified by preparative
TLC (hexane:ether ) 5:1) to give a pure product 9. The
enantiomeric excess was determined by HPLC (Chiralcel OD-
H, 0.5 mL/min, hexane:2-propanol ) 98:2). The absolute con-
figuration was determined by the specific rotation.3a,b,m
45.6, 37.9, 34.3, 30.0, 27.3, 23.4, 20.5. Anal. Calcd for C29H31
-
OPS: C, 75.97; H, 6.80. Found: C, 75.68; H, 6.53. MS m/z: 458
(M+).
(1R,3S,5S,8S)-11,11-Dim et h yl-4-oxa -5-(2-d ip h en ylp h os-
p h in o)p h en yl-6-t h ia t r icyclo[6.2.1.03,8]u n d eca n e (5). (1S)-
(-)-10-Mercaptoborneol 4 (100 mg, 0.54 mmol), 2-(diphenylphos-
phino)benzaldehyde 2 (157 mg, 0.54 mmol), p-toluenesulfonic
acid monohydrate (10 mg, 0.054 mmol), and benzene (10 mL)
were placed in a flask equipped with a Dean-Stark trap. The
mixture was refluxed for 3 h. The solvent was evaporated under
a reduced pressure, and the residue was purified by preparative
TLC (hexane:ether ) 6:1) to give a pure 5 (213 mg) in 87% yield.
mp 56-58 °C, [R]23D ) 40.9 (c 1.10, CHCl3). IR (film) cm-1: 748,
1
721, 694. H NMR (CDCl3) δ: 7.90 (m, 1H), 7.41 (m, 1H), 7.27-
7.33 (m, 10H), 7.21 (m, 1H), 6.95 (m, 1H), 6.56 (d, J ) 8.4 Hz,
1H), 3.79 (m, 1H), 3.17 (d, J ) 12.1 Hz, 1H), 2.75 (m, 1H), 2.43
(d, J ) 12,1, 1H), 2.10 (m, 1H), 1.68-1.75 (m, 2H), 1.40 (m, 1H),
1.30 (m, 1H), 1.02 (dd, J ) 13.6, 4.8 Hz, 1H), 0.90-0.97 (m, 6H).
13C NMR(CDCl3) δ: 143.6, 143.2, 136.8, 136.5, 136.4, 133.7,
133.5, 133.4, 133.2, 129.5, 128.6, 128.5, 128.4, 128.3, 128.2, 128.1,
127.6, 127.5, 84.2, 83.1, 82.6, 44.7, 44.1, 34.3, 33.2, 27.9, 25.9,
Typ ica l P r oced u r e of P d -Ca ta lyzed Asym m etr ic Allyl-
a tion of Cin n a m yl Aceta te (10) w ith Dim eth yl Ma lon a te.
A mixture of ligands 3 or 5 (5.23 mg, 0.0114 mmol) and [PdCl-
(η3-C3H5)]2 (2.09 mg, 0.0057 mmol) in dry dichloromethane (1
mL) was stirred at room temperature for 1 h, and the resulting
yellow solution was added to a mixture of acetate 10 (100 mg,
0.57 mmol) and potassium acetate (1.1 mg, 0.011 mmol) in dry
dichloromethane (1 mL), followed by the addition of dimethyl
malonate (226 mg, 1.71 mmol) and BSA (348 mg, 1.71 mmol).
The mixture was stirred at the temperature as shown in Table
2, diluted with ether, and quenched with sat. NH4Cl. The organic
layer was washed with brine, dried over MgSO4, and concen-
trated under a reduced pressure. The crude product was purified
by column chromatography on silica gel with hexane/AcOEt
(5:1) as an eluent to afford a mixture of 11 and 12. The
enantiomeric excess of 11 was determined by HPLC (Chiralcel
OJ , 0.5 mL/min, hexane:2-propanol ) 93:7). The absolute
configuration was determined by the specific rotation.3g,m
19.6, 18.7. Anal. Calcd for
C29H31OPS: C, 75.97; H, 6.80.
Found: C, 75.72; H, 6.86. MS m/z: 458 (M+).
(1R,3R,6R)-5,5,9-Tr im eth yl-2-oxa -3-(2-d ip h en ylp h osp h i-
n o)p h en yl-4-th ia bicyclo[4.4.0]d eca n e (7). 3,7,7-Trimethyl-
7-mercaptomenthol 6 (100 mg, 0.54 mmol), 2-(diphenylphosphino)-
benzaldehyde 2 (157 mg, 0.54 mmol), p-toluenesulfonic acid
monohydrate (10 mg, 0.054 mmol), and toluene (10 mL) were
placed in a flask equipped with a Dean-Stark trap. The mixture
was refluxed for 6 h. The solvent was evaporated under a
reduced pressure, and the residue was purified by preparative
TLC (hexane: ether ) 40:1) to give a pure 7 (75 mg) in 30%
yield. mp 55-57 °C, [R]23 ) -33.3 (c 2.10, CHCl3). IR (film)
D
cm-1: 745, 717, 706. 1H NMR (CDCl3): δ (CDCl3): 7.76 (m, 1H),
7.25-7.39 (m, 11H), 7.17 (t, J ) 7.4 Hz, 1H), 6.89 (m, 1H), 6.61