NMR (202 MHz, CDCl3): d 113.52 (d, P1, JP1,P2 = 2.03 Hz),
121.17 (d, P2, JP1,P2 = 2.03 Hz). MS (DCI, m/z) 461 (M +
H+, 100). HRMS (ES+, m/z) calcd. for C28H31O2P2 (M + H+)
461.1799, found 461.1831. Single crystals were obtained by slow
evaporation of dichloromethane.
C–P2), 138.19 (d, JC,P1 = 15.09 Hz, C–P1), 142.97 (s, Cipso),
142.97 (s, Ph), 143.61 (d, JC,P1 = 12.58 Hz, Ph–C–P1), 144.13
(d, JC,P2 = 12.58 Hz, Ph–C–P2), 144.47 (d, JC,P1 = 17.61 Hz,
CH3–C–C), 144.85 (d, JC,P2 = 17.61 Hz, CH3–C–C), 145.22 (d,
JC,P1 = 12.58 Hz, CH3–C–C–Ph), 145.58 (d, JC,P2 = 16.36 Hz,
1
CH3–C–C–Ph). 31P{ H} NMR (202 MHz, CDCl3): d 117.48 (d,
(-)-3,3¢,4,4¢-Tetramethyl-5,5¢-diphenyl-1,1¢-(pentane-2,4-dioxy)-
2,2¢-biphosphole, 4b. Obtained from (2S,4S)-(+)-pentaned◦iol.
P1, JP1,P2 = 2.03 Hz), 121.10 (d, P2, JP1,P2 = 2.03 Hz). MS (DCI,
m/z) 523 (M + H+, 100). HRMS (ES+, m/z) calcd. for C33H33O2P2
(M + H+) 523.1956, found 523.1931.
Yellow solid. Yield: 71% (0.353 mg, 0.745 mmol). mp = 228 C.
1
[a]25 = - 317.0 (c 0.3, CH2Cl2). H NMR (500 MHz, CDCl3):
D
(+)-3,3¢,4,4¢-Tetramethyl-5,5¢-diphenyl-1,1¢-(3-phenylpropane-
1,3-dioxy)-2,2¢-biphosphole, 4c¢. Obtained from (R)-(-)-1-
phenyl-1,3-propanediol. Yellow solid. Yield: 86% (0.471 mg,
d 0.68 (d, JH,H = 6.16 Hz, 6H, CH3), 1.20 (m, 2H, CH2), 2.16
(d, JH,P = 6.16 Hz, 6H, CH3–C–C), 2.20 (d, JH,P = 4.90 Hz, 6H,
CH3–C–CPh), 3.56 (m, 2H, CH–O), 7.25 (m, 2H, Ph), 7.41 (m,
◦
0.903 mmol). mp = 236 C. [a]25 = + 526.8 (c 0.2, CH2Cl2).
4H, Ph), 7.52 (m, 4H, Ph). 13C{ H} NMR (125 MHz, CDCl3): d
1
D
1H NMR (200 MHz, CDCl3): d 1.37 (m, 1H, CH2), 1.58 (m,
1H, CH2), 2.00 (d, JH,P2 = 5.00 Hz, 3H, CH3–C–C), 2.16 (d,
JH,P2 = 5.00 Hz, 3H, CH3–C–C), 2.21 (m, 6H, CH3–C–CPh),
3.48 (m, 2H, CH2–O–P2), 4.40 (m, 1H, CH–O–P1), 7.28 (m,
14.82 (s, CH3–C–CPh), 15.70 (d, JC,P = 7.09 Hz, CH3–C–C), 22.74
(s, CH3), 46.87 (s, CH2), 73.71 (d, JC,P = 13.81 Hz, CH–O), 125.95
(s, Ph), 128.46 (s, Ph), 128.89 (d, JC,P = 10.39 Hz, Cortho), 137.37
(dd, JC,P = 16.05 Hz, JC,P = 14.07 Hz, C–P), 137.63 (d, JC,P
=
15H, Ph). 31P{ H} NMR (81 MHz, CDCl3): d 117.56 (s, P1),
1
18.19 Hz, Cipso), 143.06 (d, JC,P = 13.42 Hz, Ph–C–P), 144.07 (d,
121.18 (s, P2).
JC,P = 18.79 Hz, CH3–C–C), 144.40 (dd, JC,P = 16.15 Hz, JC,P
=
1.58 Hz CH3–C–C–Ph). 31P{ H} NMR (202 MHz, CDCl3): d
113.67 (s). MS (DCI, m/z) 475 (M + H+, 100%). HRMS (ES+,
m/z) calcd. for C29H33O2P2 (M + H+) 475.1956, found 475.1956.
1
(-)-3,3¢,4,4¢-Tetramethyl-5,5¢-diphenyl-1,1¢-(1,3-diphenyl-
propane-1,3-dioxy)-2,2¢-biphosphole, 4d. Obtained from (1S,3S)-
(-)-1,3-diphenylpropane-1,3-diol. Yellow solid. Yield: 85%
◦
(0.534 mg, 0.893 mmol). mp = 256 C (decomposed). [a]25
=
D
S[Rp,Rp,Rc,Rc]-(+)-3,3¢,4,4¢-Tetramethyl-5,5¢-diphenyl-1,1¢-
-278.5 (c 0.1, CH2Cl2). 1H NMR (500 MHz, CDCl3): d 1.56 (m,
(pentane-2,4-dioxy)-2,2¢-biphosphole,
4b¢. Obtained
from
2H, CH2), 2.06 (d, JH,P = 2.19 Hz, 6H, CH3–C–C), 2.26 (d, JH,P
=
(2R,4R)-(-)-pentanediol.◦ Yellow solid. Yield: 82% (0.468 mg,
2.19 Hz, 6H, CH3–C–CPh), 4.54 (m, 2H, CH–O), 6.88 (m, 13H,
0.861 mmol). mp = 223 C. [a]25 = + 338.5 (c 0.1, CH2Cl2). 1H
D
1
Ph), 6.99 (m, 7H, Ph). 13C{ H} NMR (125 MHz, CDCl3): d 14.5 (s,
NMR (500 MHz, CDCl3): d 0.67 (d, JH,H = 6.20 Hz, 6H, CH3),
1.21 (m, 2H, CH2), 2.15 (d, JH,P = 6.20 Hz, 6H, CH3–C–C), 2.20
(d, JH,P = 5.02 Hz, 6H, CH3–C–CPh), 3.54 (m, 2H, CH–O), 7.25
CH3–C–CPh), 15.99 (d, JC,P = 7.55 Hz, CH3–C–C), 50.69 (s, CH2),
78.2 (d, JC,P = 2.6 Hz, CH), 124.72 (s, Ph), 125.12 (s, Ph), 126.37
(s, Ph), 127.61 (s, Ph), 127.69 (s, Ph), 128.33 (d, JC,P = 11.32 Hz,
Cortho), 136.78 (m, C–P), 142.55 (s, Cipso), 143.61 (d, JC,P = 12.58 Hz,
1
(m, 2H, Ph), 7.41 (m, 4H, Ph), 7.51 (m, 4H, Ph). 13C{ H} NMR
(125 MHz, CDCl3): d 14.86 (s, CH3–C–CPh), 15.74 (d, JC,P
=
Ph–C–P), 144.54 (d, JC,P = 17.61 Hz, CH3–C–C), 145.69 (d, JC,P
=
7.15 Hz, CH3–C–C), 22.75 (s, CH3), 46.82 (m, CH2), 73.72 (d,
JC,P = 13.80 Hz, CH–O), 125.95 (s, Ph), 128.48 (s, Ph), 128.89 (d,
JC,P = 10.38 Hz, Cortho), 137.36 (d, JC,P = 15.92 Hz, C–P), 137.61
(d, JC,P = 18.28 Hz, Cipso), 143.12 (d, JC,P = 13.23 Hz, Ph–C–P),
144.01 (d, JC,P = 18.80 Hz, CH3–C–C), 144.45 (d, JC,P = 15.93 Hz,
1
16.36 Hz, CH3–C–C–Ph). 31P{ H} NMR (202 MHz, CDCl3): d
117.65 (s). MS (DCI, m/z) 599 (M + H+, 100). HRMS (ES+, m/z)
calcd. for C39H37O2P2 (M + H+) 599.2269, found 599.2257.
(-)-3,3¢,4,4¢-Tetramethyl-5,5¢-diphenyl-1,1¢-(hexane-2,5-dioxy)-
2,2¢-biphosphole, 4e. Obtained from (2S,4S)-(+)-hexaned◦iol.
1
CH3–C–C–Ph). 31P{ H} NMR (202 MHz, CDCl3): d 113.51
(s). MS (DCI, m/z) 475 (M + H+, 100%). HRMS (ES+, m/z)
calcd. for C29H33O2P2 (M + H+) 475.1956, found 475.1946. Single
crystals were obtained by slow evaporation of dichloromethane.
Yellow solid. Yield: 85% (0.436 mg, 0.893 mmol). mp = 229 C.
1
[a]25 = -357.8 (c 0.2, CH2Cl2). H NMR (500 MHz, CDCl3):
D
d 0.80 (d, JH,H = 10.00 Hz, 6H, CH3), 1.02 (m, 2H, CH2), 1.67
(m, 2H, CH2), 2.20 (d, JH,P = 5.00 Hz, 6H, CH3–C–C), 2.27 (d,
JH,P = 5.00 Hz, 6H, CH3–C–CPh), 3.72 (m, 2H, CH–O), 7.29
(-)-3,3¢,4,4¢-Tetramethyl-5,5¢-diphenyl-1,1¢-(3-phenylpropane-
1,3-dioxy)-2,2¢-biphosphole, 4c. Obtained from (S)-(+)-1-
phenyl-1,3-propanediol. Yellow solid. Yield: 86% (0.471 mg,
(m, 2H, Ph), 7.42 (m, 4H, Ph), 7.51 (m, 4H, Ph). 13C{ H} NMR
1
(125 MHz, CDCl3): d 14.99 (s, CH3–C–CPh), 15.99 (d, JC,P
=
◦
0.903 mmol). mp = 232 C. [a]25 = -524.2 (c 0.2, CH2Cl2).
D
13.84 Hz, CH3–C–C), 21.73 (d, JC,P = 2.51 Hz, CH3), 27.46 (s,
CH2), 78.29 (d, JC,P = 13.84 Hz, CH–O), 125.91 (s, Ph), 128.53 (s,
Ph), 128.73 (d, JC,P = 8.80 Hz, Cortho), 137.57 (d, JC,P = 17.61 Hz,
1H NMR (500 MHz, CDCl3): d 1.40 (m, 1H, CH2), 1.61 (m,
1H, CH2), 2.04 (d, JH,P2 = 4.95 Hz, 3H, CH3–C–C), 2.20 (d,
JH,P1 = 4.91 Hz, 3H, CH3–C–C), 2.23 (d, JH,P2 = 5.55 Hz, 3H,
CH3–C–CPh), 2.25 (d, JH,P1 = 5.15 Hz, 3H, CH3–C–CPh), 3.50
(m, 2H, CH2–O–P2), 4.45 (m, 1H, CH–O–P1), 6.95 (m, 7H,
Ph), 7.02 (m, 3H, Ph), 7.30 (m, 1H, Ph), 7.50 (m, 4H, Ph).
C–P), 140.38 (d, JC,P = 16.35 Hz, Ph–C–P), 142.23 (d, JC,P
=
15.10 Hz, CH3–C–C), 142.81 (d, JC,P = 16.35 Hz, CH3–C–C–Ph).
31P{ H} NMR (202 MHz, CDCl3): d 104.25 (s). MS (DCI, m/z)
1
489 (M + H+, 100).
13C{ H} NMR (125 MHz, CDCl3): d 14.56 (s, CH3–C–C, P2),
1
14.85 (s, CH3–C–C, P1), 15.94 (s, CH3–C–CPh, P1), 16.00 (s,
CH3–C–CPh, P2), 41.08 (s, CH2), 64.88 (d, JC,P2 = 13.75 Hz,
CH2–O), 77.30 (m, CH–O), 124.70 (s, Ph), 125.12 (s, Ph), 126.29
(s, Ph), 126.36 (s, Ph), 127.54 (s, Ph), 127.68 (s, Ph), 128.30 (s,
Ph), 128.37 (s, Ph), 128.55 (s, Ph), 128.61 (s, Ph), 128.67 (s, Ph),
136.80 (d, JC,P = 17.61 Hz, Cortho), 137.16 (d, JC,P2 = 17.61 Hz,
(+)-3,3¢,4,4¢-Tetramethyl-5,5¢-diphenyl-1,1¢-(2,7-dimethyl-
octane-3,6-dioxy)-2,2¢-biphosphole, 4f. Obtained from (3S,6S)-
2,7-dimethyl-3,6-octanediol. Orange solid. Yield: 83% (0.474 mg,
0.872 mmol). mp = 203 ◦C. [a]25 = + 202.0 (c 0.1, CH2Cl2). 1H
D
NMR (500 MHz, CDCl3): d 0.40 (d, JH,H = 5.00 Hz, 6H, CH3),
0.46 (d, JH,H = 5.00 Hz, 6H, CH3), 0.95 (d, JH,H = 5.00 Hz, 4H,
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The Royal Society of Chemistry 2009
Dalton Trans., 2009, 6528–6535 | 6533
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