3
52 Bull. Chem. Soc. Jpn., 77, No. 2 (2004)
Hydroesterification of Vinylarenes
0
0
7
3
1
1
1
2
.46–7.38 (m, 2H), 7.29–7.09 (m, 4H), 6.91 (d, J ¼ 8:2 Hz, 1H),
(S)-(ꢀ)-2-Dicyclohexylphosphino-2 -benzyloxy-1,1 -binaph-
1
3
.73 (s, 3H), 2.26–0.80 (m, 18H); C NMR (68 MHz, CDCl3) ꢁ
54.0, 142.0, 141.5, 137.9, 134.1, 133.4, 132.9, 132.8, 129.5,
28.3, 128.2, 127.7, 127.2, 126.9, 126.8, 125.9, 125.7, 123.0,
22.2, 112.2, 55.4, 31.5, 31.2, 30.9, 30.8, 26.8, 26.7, 26.3, 26.2,
6.0, 25.9, 25.6, 25.5 (multiplet due to complex P–C coupling);
P NMR (81 MHz, CDCl3) ꢁ ꢂ8:2; IR (KBr) 2949, 2862, 1510,
thyl (1c). Yield: 9% (2 steps from (S)-2-dicyclohexylphosphino-
0
0
ꢁ
yl-2 -hydroxy-1,1 -binaphthyl) as a colorless solid, mp 90–91 C,
2
2
1
½ꢀꢃ
ꢂ64 (c 0.50, CH2Cl2). H NMR (200 MHz, CDCl3) ꢁ
D
1
3
8.05–6.73 (m, 17H), 5.05 (s, 2H), 2.07–0.80 (m, 22H); C NMR
(68 MHz, CDCl3) ꢁ 153.4, 137.3, 134.1, 133.4, 133.2, 133.1,
129.3, 129.0, 128.7, 128.6, 128.3, 127.9, 127.7, 127.6, 127.4,
127.2, 127.0, 126.8, 126.5, 126.3, 126.1, 126.0, 125.7, 123.5,
123.3, 114.1, 70.0, 35.4, 35.1, 34.6, 34.4, 30.6, 30.4, 30.2, 30.0,
29.8, 27.3, 26.9, 26.8, 26.4, 25.8 (observed complexity due to P–
C splitting); 31P NMR (81 MHz, CDCl3) ꢁ ꢂ6:6; IR (KBr) 2922,
2847, 1622, 1593, 1499, 1447, 1267, 1219, 1070, 1020, 804,
3
1
ꢂ1
1
269, 1250, 1082, 806, 743 cm ; HRMS Calcd for C31H34P:
þ
MH 453.2347. Found: m=z 453.2350.
0
(
S)-2-Dicyclohexylphosphinoyl-2 -trifluoromethylsulfonyl-
oxy-1,1 -binaphthyl. Prepared according to the literature20 as a
colorless solid, Rf 0.29 (ethyl acetate). 1H NMR (200 MHz,
CDCl3) ꢁ 8.10–7.91 (m, 5H), 7.62–7.42 (m, 4H), 7.39–7.19 (m,
0
ꢂ1
þ
745, 694 cm ; HRMS Calcd for C39H42OP: MH 557.2973.
Found: m=z 557.2966.
3
1
2
H), 7.12 (d, J ¼ 7:9 Hz, 1H), 2.19–0.80 (m, 22H); P NMR
0
0
(
81 MHz, CDCl3) ꢁ 48.7.
(S)-(ꢀ)-2-Dicyclopentylphosphinoyl-2 -isopropoxy-1,1 -bi-
0
0
1
(
1a).
S)-2-Dicyclohexylphosphino-2 -methoxy-1,1 -binaphthyl
naphthyl. Colorless solid, Rf 0.43 (ethyl acetate). H NMR (200
20
31
(
The prepared sample exhibited P NMR (81 MHz,
MHz, CDCl3) ꢁ 7.90–7.68 (m, 5H), 7.43–7.28 (m, 2H), 7.25–7.02
(m, 4H), 6.86 (d, J ¼ 8:6 Hz, 1H), 4.47 (m, J ¼ 6:0 Hz), 2.21–1.95
(br, 2H), 1.95–1.62 (br, 2H), 1.60–1.20 (br, 14H), 1.04 (d, J ¼ 6:0
CDCl3) ꢁ ꢂ6:7.
Ligands 1a–c, 2b–d, and 3a–b were also prepared according to
methods described above:
3
1
Hz, 3H), 0.75 (d, J ¼ 6:0 Hz, 3H); P NMR (81 MHz, CDCl3) ꢁ
0
0
þ
(
S)-(ꢀ)-2-Dicyclohexylphosphinoyl-2 -isopropoxy-1,1 -bi-
50.5. HRMS (FAB) Calcd for C33H38O2P: MH 497.2609. Found:
m=z 497.2610.
ꢁ
24
1
naphthyl. Mp 39–40 C, ½ꢀꢃ
ꢂ49 (c 0.50, CH2Cl2). H NMR
D
0
0
(
(
200 MHz, CDCl3) ꢁ 8.13–7.81 (m, 5H), 7.54–7.08 (m, 6H), 6.90
d, J ¼ 8:1 Hz, 1H), 4.50 (septet, J ¼ 6:0 Hz, 1H), 1.90–0.85 (m,
(S)-(ꢀ)-2-Dicyclopentylphosphino-2 -isopropoxy-1,1 -bi-
naphthyl (2b). Yield: 55% (2 steps from (S)-2-dicyclopentyl-
0
0
2
1
2H), 1.12 (d, J ¼ 6:0 Hz, 3H), 0.74 (d, J ¼ 6:0 Hz, 3H);
C NMR (68 MHz, CDCl3) ꢁ 153.5, 134.5, 134.11, 134.08,
33.1, 129.6, 128.6, 128.3, 128.1, 127.7, 127.6, 127.0, 126.8,
26.6, 125.9, 125.6, 123.4, 123.0, 122.9, 116.3, 71.5, 37.9, 37.8,
6.9, 36.8, 26.6, 26.53, 26.47, 26.4, 26.3, 26.2, 26.12, 26.05,
5.8, 25.7, 22.8, 22.1 (multiplet due to complex P–C coupling);
P NMR (81 MHz, CDCl3) ꢁ 48.9; IR (KBr) 2924, 2849, 1447,
phosphinoyl-2 -hydroxy-1,1 -binaphthyl) as a colorless solid, mp
22
3
ꢁ
136–137 C, Rf 0.55 (hexane–ethyl acetate = 10:1), ½ꢀꢃ
D
1
1
1
3
2
ꢂ101 (c 0.5, CH2Cl2). H NMR (200 MHz, CDCl3) ꢁ 7.96–7.68
(m, 7H), 7.44–7.28 (m, 3H), 7.26–6.98 (m, 5H), 6.86 (d, J ¼ 8:2
Hz, 1H), 4.48 (m, 1H), 2.41–1.95 (br, 2H), 1.87–1.62 (br, 2H),
1.60–1.19 (br, 14H), 1.04 (d, J ¼ 6:0 Hz, 3H), 0.74 (d, J ¼ 5:8
3
1
13
Hz, 3H); C NMR (68 MHz, CDCl3) ꢁ 152.9, 134.5, 129.1,
ꢂ1
1
263, 1242, 1111, 1003, 806, 746 cm ; HRMS Calcd for
þ
128.4, 128.2, 127.6, 127.5, 127.1, 126.9, 126.2, 125.9, 125.5,
123.1, 115.5, 79.6, 70.5, 39.1, 31.6, 31.3, 30.9, 26.8, 26.7, 26.3,
26.2, 25.8, 25.74, 25.69, 25.57, 22.6, 22.2; 31P NMR (81 MHz,
CDCl3) ꢁ ꢂ8:8; IR (KBr) 2950, 2864, 1622, 1591, 1508, 1448,
C35H42O2P: MH 525.2922. Found: m=z 525.2922.
0
0
(
naphthyl (1b). Yield: 11% (2 steps from (S)-2-dicyclohexylphos-
phinoyl-2 -hydroxy-1,1 -binaphthyl) as a colorless solid, mp 117–
S)-(ꢀ)-2-Dicyclohexylphosphino-2 -isopropoxy-1,1 -bi-
0
0
ꢂ1
1265, 1242, 1109, 1001, 806, 746 cm ; HRMS (FAB) Calcd for
ꢁ
22
1
þ
1
ꢁ
4
18 C, ½ꢀꢃ
ꢂ98 (c 0.50, CH2Cl2). H NMR (200 MHz, CDCl3)
C33H38OP: MH 481.2660. Found: m=z 481.2662.
D
0
0
7.97–7.60 (m, 5H), 7.55–6.95 (m, 6H), 6.85 (d, J ¼ 8:4 Hz, 1H),
.45 (sept, J ¼ 6:0 Hz, 1H), 1.86–0.60 (m, 22H), 1.03 (d, J ¼ 6:0
(S)-(ꢀ)-2-Dicyclopentylphosphinoyl-2 -benzyloxy-1,1 -bi-
naphthyl. Colorless solid, Rf 0.17 (hexane–ethyl acetate = 1:9).
1
1
3
Hz, 3H), 0.74 (d, J ¼ 6:0 Hz, 3H); C NMR (68 MHz, CDCl3) ꢁ
H NMR (200 MHz, CDCl3) ꢁ 8.06 (dd, J ¼ 8:6, 1.3 Hz, 1H), 7.84
1
1
1
2
52.9, 143.7, 143.3, 134.4, 133.2, 133.1, 129.0, 128.9, 128.3,
27.6, 127.4, 127.0, 126.4, 126.3, 126.1, 125.9, 125.4, 125.3,
23.0, 115.3, 70.3, 35.2, 34.8, 30.7, 30.4, 30.2, 30.0, 27.4, 27.2,
6.5, 26.4, 25.8, 22.7, 22.1 (multiplet due to complex P–C cou-
(d, J ¼ 7:9 Hz, 1H), 7.55 (ddd, J ¼ 7:9, 6.5, 1.3 Hz, 1H), 7.45–
7.18 (m, 5H), 6.94 (d, J ¼ 8:6 Hz, 1H), 6.83 (d, J ¼ 7:6 Hz,
1
3
1H); C NMR (68 MHz, CDCl3) ꢁ 173.2, 153.8, 138.0, 137.9,
136.3, 134.5, 134.4, 134.2, 133.0, 132.8, 130.3, 128.5, 128.4,
128.3, 128.0, 127.8, 127.6, 127.4, 127.3, 126.7, 126.5, 126.4,
126.2, 125.4, 123.8, 121.5, 114.6, 70.6, 38.9 (d, J ¼ 42 Hz), 37.8
(d, J ¼ 42 Hz), 27.8, 26.6, 26.5, 26.4, 26.2, 26.1, 25.6, 25.4,
25.3, 25.2, 21.3; 31P NMR (81 MHz, CDCl3) ꢁ 50.8. HRMS
pling); 31P NMR (81 MHz, CDCl3) ꢁ ꢂ6:7; IR (KBr) 2924,
2
8
849, 1622, 1591, 1506, 1447, 1369, 1325, 1265, 1244, 1001,
þ
ꢂ1
12, 746 cm ; HRMS Calcd for C35H42OP: MH 509.2973.
Found: m=z 509.2976.
S)-(ꢀ)-2-Dicyclohexylphosphinoyl-2 -benzyloxy-1,1 -bi-
0
0
þ
(
(FAB) Calcd for C37H38O2P: MH 545.2609. Found: m=z
545.2601.
ꢁ
23
1
naphthyl. Mp 74–75 C, ½ꢀꢃ
ꢂ60 (c 0.50, CH2Cl2). H NMR
D
0
0
(
(
5
200 MHz, CDCl3) ꢁ 8.06–7.83 (m, 5H), 7.59–7.02 (m, 9H), 6.95
d, J ¼ 8:8 Hz, 1H), 6.88–6.78 (m, 2H), 5.09 (d, J ¼ 12:3 Hz, 1H),
(S)-(ꢀ)-2-Dicyclopentylphosphino-2 -benzyloxy-1,1 -bi-
naphthyl (2c). Yield: 58% (2 steps from (S)-2-dicyclopentylphos-
0
22
1
3
0
.01 (d, J ¼ 12:3 Hz, 1H), 1.88–0.40 (m, 22H); C NMR (68
phinoyl-2 -hydroxy-1,1 -binaphthyl) as a colorless solid, mp 154–
ꢁ
MHz, CDCl3) ꢁ 153.7, 136.8, 129.8, 128.3, 128.2, 128.1, 127.95,
156 C, Rf 0.38 (hexane–ethyl acetate = 10:1), ½ꢀꢃ
ꢂ44 (c 0.5,
D
1
1
1
1
2
27.91, 127.86, 127.7, 127.6, 127.22, 127.17, 127.0, 126.9,
26.84, 126.76, 126.7, 126.53, 126.46, 126.3, 126.0, 125.8,
25.6, 123.5, 114.8, 70.7, 38.0, 37.8, 37.1, 36.9, 26.9, 26.8, 26.6,
6.4, 26.3, 26.1, 25.9, 25.8, 25.6, 25.4 (multiplet due to complex
CH2Cl2). H NMR (200 MHz, CDCl3) ꢁ 8.02–7.63 (m, 3H), 7.50–
6.80 (m, 14H), 4.74 (d, J ¼ 11:9 Hz, 1H), 4.59 (d, J ¼ 11:9 Hz,
1H), 2.18–0.82 (m, 18H); 13C NMR (68 MHz, CDCl3) ꢁ 153.2,
137.3, 135.3, 134.2, 133.4, 131.6, 131.4, 130.3, 129.3, 127.9,
127.7, 127.6, 127.3, 127.1, 127.0, 126.9, 126.3, 126.0, 123.3,
122.3, 70.1, 39.0, 38.9, 31.5, 30.9, 26.6, 26.5, 26.3, 26.2, 25.7;
3
1
P–C coupling); P NMR (81 MHz, CDCl3) ꢁ 49.0; IR (KBr)
926, 2851, 1508, 1448, 1267, 1217, 1148, 1022, 814, 746, 694
2
ꢂ1
þ
31
cm ; HRMS Calcd for C39H42O2P: MH 573.2922. Found: m=z
73.2913.
P NMR (81 MHz, CDCl3) ꢁ ꢂ8:8; IR (KBr) 2960, 2860, 1622,
ꢂ1
5
1591, 1506, 1452, 1417, 1261, 1221, 1020, 802, 744 cm ; HRMS