T.-Z. Zhang et al. / Tetrahedron: Asymmetry 18 (2007) 251–259
257
N, 1.81. Found: C, 65.27; H, 5.88; N, 1.49. Compound (R)-
8.03–7.96 (m, 2H), 7.74 (d, J = 8.3 Hz, 1H), 7.66–7.58
(m, 3H), 7.48–7.33 (m, 7H), 6.96 (d, J = 8.8 Hz, 1H),
6.88 (d, J = 12.7 Hz, 1H), 6.69 (s, 2H), 6.59 (m, 3H), 6.45
(d, J = 7.8 Hz, 1H), 4.67 (m, 1H), 4.43 (m, 1H), 3.49–
20
8
a. ½aꢁ ¼ þ15:1 (c 1.0, CHCl ), mp 187–188 ꢁC, ee = 99%
D
3
by HPLC analysis Chiralcel OD column, hexane/isopropa-
nol = 95:5, flow rate 0.7 mL/min, tR1 = 7.77 min (major),
tR2 = 9.39 min (minor).
3
1
2.82 (m, 13H), 2.16 d, J = 6.4 Hz, 3H);
P NMR
(
161.92 MHz, CDCl ) 26.3 ppm; MALDIMS m/z: 832.0
3
3
1
+
Compound (S ,S)-12a (48% yield), >98% de by P NMR.
(M ꢀCl); IR (KBr): 2924, 1687, 1608, 1502, 1398, 1324,
p
20
ꢀ1
Complex (S ,S)-12a, ½aꢁ ¼ ꢀ163:9 (c 0.60, CHCl ), mp
1169, 1128, 1061, 1016, 939, 830, 700, 601, 531 cm . Anal.
p
D
3
1
1
(
67–170 ꢁC. H NMR (300 MHz, CDCl ): d 7.81–7.63
Calcd for C H ClF NPPd: C, 60.84; H, 4.53; N, 1.61.
Found: C, 61.22; H, 4.67; N, 1.53. Compound (R)-8c.
3
44 39
6
m, 6H), 7.45–7.37 (m, 2H), 7.26–7.13 (m, 8H), 6.96 (dd,
20
J = 11.2, 1.7 Hz, 1H), 6.64–6.56 (m, 5H), 6.08 (m, 1H),
.42 (m, 2H), 3.06 (m, 1H), 2.91–2.76 (m, 12H), 2.21 (d,
NMR (161.92 MHz, CDCl3)
2.7 ppm; MALDIMS m/z (relative intensity %): 696
½aꢁ ¼ þ11:0 (c 0.32, CHCl ), mp 143–145 ꢁC, ee = 98%
D
3
4
by HPLC analysis Chiralcel OD column, hexane/isopropa-
nol = 95:5, flow rate 0.7 mL/min, tR1 = 9.72 min (major),
tR2 = 11.30 min (minor).
3
1
J = 6.5 Hz, 3H);
P
3
(
+
M ꢀCl); IR (KBr): 2922, 2851, 1735, 1573, 1435, 1184,
ꢀ
1
31
Compound (S ,S)-12c (47% yield), >98% de by P NMR.
1
093, 938, 796, 740, 693, 578, 530, 512, 424 cm . Anal.
p
2
0
Calcd for C H ClNPPdÆ1/2CH Cl : C, 65.86; H, 5.46;
N, 1.81. Found: C, 66.01; H, 5.87; N, 1.52. Compound
Complex (S ,S)-12c, ½aꢁ ¼ ꢀ141:5 (c 1.14, CHCl ), mp
4
2
41
2
2
p
D
3
1
155–156 ꢁC. H NMR (300 MHz, CDCl ): d 7.83–7.62
3
2
D
0
(
S)-8a. ½aꢁ ¼ ꢀ15:1 (c 1.0, CHCl ), mp 187–188 ꢁC,
(m, 6H), 7.52–7.24 (m, 8H), 6.86 (m, 2H), 6.68 (m, 3H),
6.56 (m, 1H), 6.16 (d, J = 7.4 Hz, 1H), 4.52–4.40 (m,
2H), 3.71 (m, 1H), 3.41–3.26 (m, 2H), 3.10 (d, J =
3.3 Hz, 3H), 3.03–2.85 (m, 7H), 2.22 (d, J = 4.3 Hz, 3H);
3
ee = 99% by HPLC analysis Chiralcel OD column,
hexane/isopropanol = 95:5, flow rate 0.7 mL/min,
tR1 = 7.08 min (minor), tR2 = 8.52 min (major).
3
1
P NMR (161.92 MHz, CDCl ) 30.7 ppm; MALDIMS
3
0
+
4
.9.2. Resolution of di(4 -methoxyphenyl)([2.2]paracyclo-
phane-4-yl)phosphine (±)-8b. Compound (R ,S)-12b was
obtained as yellow crystals (44% yield), >98% de by
m/z: 832.0 (M ꢀCl); IR (KBr): 2924, 2854, 1687, 1608,
1502, 1398, 1324, 1169, 1128, 1061, 1016, 938, 829, 700,
p
3
1
ꢀ1
P
601, 507 cm . Anal. Calcd for C H ClF NPPdÆ CH Cl :
C, 58.66; H, 4.43; N, 1.54. Found: C, 58.38; H, 4.54; N,
4
4
39
6
2
2
20
NMR; complex (R ,S)-12b, ½aꢁ ¼ ꢀ30:2 (c 0.78, CHCl ),
p
D
3
1
20
mp 191–193 ꢁC. H NMR (300 MHz, CDCl ): d 7.84–7.73
1.58. Compound (S)-8c. ½aꢁ ¼ ꢀ11:2 (c 0.27, CHCl ),
3
D
3
(
(
(
m, 3H), 7.64 (d, J = 7.9 Hz, 1H), 7.41–7.31 (m, 4H), 6.99
d, J = 8.8 Hz, 1H), 6.97 (d, J = 8.5 Hz, 2H), 6.79–6.63
m, 6H), 6.47 (s, 2H), 6.22 (s, 1H), 4.84 (m, 1H), 4.36 (m,
mp 143–145 ꢁC, ee = 98% by HPLC analysis Chiralcel
OD column, hexane/isopropanol = 95:5, flow rate 0.7
mL/min, tR1 = 10.29 min (minor), tR2 = 11.30 min (major).
1
2
H), 3.78 (s, 3H), 3.72 (s, 3H), 3.36–3.32 (m, 2H), 2.94–
.70 (m, 10H), 2.16 (d, J = 6.5 Hz, 3H); P NMR
3
1
0
0
4.9.4. Resolution of di(3 ,5 -dimethyl)([2.2]paracyclophane-
4-yl)phosphine (±)-8d. Compound (R ,S)-12d was ob-
(
161.92 MHz, CDCl ) 26.0 ppm; MALDIMS m/z: 756.6
3
p
+
+
31
(
1
5
M ), 755.6 (M ꢀH); IR (KBr): 2924, 2853, 1683, 1594,
tained as yellow crystals (40% yield), >95% de by
P
2
0
500, 1458, 1290, 1252, 1179, 1096, 1025, 939, 798, 718,
NMR; complex (R ,S)-12d, ½aꢁ ¼ ꢀ30:1 (c 0.56, CHCl ),
p
D
3
ꢀ
1
20
1
38, 503 cm . Compound (R)-8b. ½aꢁD ¼ þ37:0 (c 0.20,
mp 173–175 ꢁC. H NMR (300 MHz, CDCl ): d 7.72 (d,
3
CHCl ), mp 122–123 ꢁC, ee = 98% by HPLC analysis Chi-
ralcel OD column, hexane/isopropanol = 95:5, flow rate 0.7
J = 8.2 Hz, 1H), 7.62–7.54 (m, 3H), 7.46–7.26 (m, 3H),
7.18 (d, J = 6.1 Hz, 2H), 7.07–6.91 (m, 3H), 6.72 (m,
2H), 6.62 (m, 2H), 6.50 (m, 2H), 6.04–5.99 (m, 1H), 5.30
3
mL/min, tR1 = 9.72 min (major), tR2 = 11.30 min (minor).
(
m, 1H), 4.33 (m, 1H), 3.38–2.66 (m, 13H), 2.23 (s, 6H),
3
1
31
Compound (S ,S)-12b (45% yield), >98% de by P NMR.
2.19 (d, J = 6.4 Hz, 3H), 2.14 (s, 6H); P NMR (161.92
p
20
Complex (S ,S)-12b, ½aꢁ ¼ ꢀ238 (c 0.97, CHCl3),
MHz, CDCl ) 25.3 ppm; MALDIMS m/z: 752.5 (MꢀCl);
p
D
3
1
mp 215–218 ꢁC. H NMR (300 MHz, CDCl ): d 7.78 (m,
IR (KBr): 2923, 2854, 1735, 1573, 1457, 1125, 938, 844,
3
ꢀ1
2
6
(
H), 7.60–7.37 (m, 6H), 7.24 (m, 2H), 6.98–6.40 (m, 10H),
805, 719, 692, 582, 563, 488 cm . Anal. Calcd for C H -
46 49
.14 (d, J = 7.9 Hz, 1H), 4.45 (m, 2H), 3.75 (s, 3H), 3.70
s, 3H), 3.66–2.75 (m, 13H), 2.21 (d, J = 5.7 Hz, 3H);
NMR (161.92 MHz, CDCl ) 30.4 ppm; MALDIMS m/z:
ClNPPdÆ1/2CH Cl : C, 67.19; H, 6.06; N, 1.69. Found: C,
2 2
20
3
1
P
67.45; H, 6.36; N, 1.43. Compound (R)-8d: ½aꢁ ¼ þ12:6 (c
D
0.45, CHCl ), mp 203–205 ꢁC, ee = 96% by HPLC analysis
3
3
+
+
7
1
4
5
56.6 (M ), 755.6 (M ꢀH); IR (KBr): 2924, 2853, 1686,
Chiralcel OD column, hexane/isopropanol = 95:5, flow rate
593, 1500, 1290, 1251, 1180, 1090, 938, 798, 720, 539,
0.7 mL/min, tR1 = 3.61 min (major), tR2 = 4.01 min (minor).
ꢀ
1
95 cm . Anal. Calcd for C H ClNO PPd: C, 66.67; H,
.72; N, 1.77. Found: C, 66.70; H, 6.06; N, 1.37. Compound
4
4
45
2
3
1
Compound (S ,S)-12d (41% yield), >95% de by P NMR.
p
2
D
0
20
(
S)-8b: ½aꢁ ¼ ꢀ37:6 (c 0.18, CHCl ), mp 122–123 ꢁC,
Complex (S ,S)-12d, ½aꢁ ¼ ꢀ231:2 (c 0.82, CHCl ), mp
3
p
D
3
1
ee = 98% by HPLC analysis Chiralcel OD column,
hexane/isopropanol = 95:5, flow rate 0.7 mL/min, tR1
185–186 ꢁC. H NMR (300 MHz, CDCl ): d 7.75 (d,
3
=
J = 8.2 Hz, 1H), 7.67 (d, J = 7.5 Hz, 1H), 7.46–7.29 (m,
1
0.29 min (minor), tR2 = 11.30 min (major).
6H), 7.08 (m, 1H), 7.00–6.93 (m, 4H), 6.63–6.49 (m, 3H),
6
.24 (m, 2H), 6.00–5.88 (m, 2H), 4.40–4.24 (m, 2H),
0
31
4
.9.3. Resolution of di(4 -trifluoromethylphenyl)([2.2]para-
3.32–2.61 (m, 13H), 2.24–2.15 (m, 15H);
P NMR
cyclophane-4-yl)phosphine (±)-8c. Compound (R ,S)-12c
(161.92 MHz, CDCl ) 27.0 ppm; MALDIMS m/z: 752.5
p
3
was obtained as yellow crystals (45% yield), >98% de
(MꢀCl); IR (KBr): 2921, 2853, 1573, 1458, 1255, 1125,
3
1
20
ꢀ1
by P NMR; complex (R ,S)-12c, ½aꢁ ¼ ꢀ5:1 (c 1.00,
1075, 938, 844, 805, 719, 692, 582, 488 cm . Compound
p
D
1
20
CHCl ), mp 138–140 ꢁC. H NMR (300 MHz, CDCl ): d
(S)-8d ½aꢁD ¼ ꢀ12:6 (c 0.40, CHCl ), mp 203–205 ꢁC,
3
3
3