299
(
R)-(S)-3c: Yield 62%. Orange viscous oil, [a]~ -225 ° (c 0.57, chloroform)
(
(
[a]~ + 183" (c 0.55, chloroform) for (S)-(R)-3e [11]). 1H NMR (CDCI3): 8 1.11
d, J 7 Hz, 3H), 1.67 (s, 6H), 3.45-3.58 (m, 2H), 3.92-4.23 (m, 4H), 4.34-4.47 (m,
2
H), 7.22-7.95 (m, 16H). 31p {1H} NMR (CDC13): 8 -22.7 (s), -16.9 (s). Anal.
Found: C, 56.26; H, 3.80; N, 1.47. C42H33NF12P2Fe talc.: C, 56.21; H, 3.71; N,
.56%. (R)-(S)-4c: Yield 18%. Orange viscous oil, [a]~ -247 ° (c 0.52, chloroform).
H NMR (CDC13): 8 1.21 (d, J 7 Hz, 3H), 1.70 (s, 6H), 3.73 (m, 1H), 3.97 (s, 5H),
.14 (dq, J 3 and 7 Hz, 1H), 4.27 (t, J 3 Hz, 1H), 4.42 (m, 1H), 7.27-7.73, 7.90-8.10
m, 8H). 31p{1H} NMR (CDCI3): 8 -21.3 (s). Anal. Found: C, 58.65; H, 4.57; N,
.39. C28H26NF6PFe calc.: C, 58.25; H, 4.54; N, 2.43%.
R)-(S)-3d: Yield 80%. Orange glassy solid, [a]~ -273 ° (c 0.73, chloroform)
[a]2D° --270 ° (C 0.49, chloroform) [11]). 1H NMR (CDCI3): 8 1.12 (d, J 7 Hz, 3H),
.70 (s, 6H), 3.35-3.51 (m, 2H), 3.88-4.20 (m, 4H), 4.24-4.43 (m, 2H), 6.74-7.66
m, 16H). 31p{1H} NMR (CDC13): 8 -26.1 (t, J 4 Hz), -20.1 (t, J 4 It2). Anal.
Found: C, 65.32; H, 4.76; N, 1.96. CasH33NF4P2Fe talc.: C, 65.44; H, 4.76; N,
.95%. (R)-(S)-4d: Yield 7%. Orange crystals (reerystanized from methanol), m.p.
2°C, [a]2D° --287 ° (C 0.70, chloroform). 1H NMR (CDCI3): 8 1.22 (d, J 7 Hz, 3H),
.73 (s, 6H), 3.78 (m, 1H), 3.94 (s, 5H), 4.13 (dq, J 3 and 7 Hz, 1H), 4.25 (t, J 3 Hz,
H), 4.38 (m, 1H), 6.78-7.68 (m, 8H). 31p{1H} NMR (CDC13): 8 -25.2 (t, J 4
Hz). Anal. Found: C, 65.23; H, 5.47; N, 2.92. C26H26NF2PFe eale.: C, 65.43; H,
.49; N, 2.93%.
R)-(S)-3e: Yield 30%. Orange glassy solid, [a]~ -312" (c 0.56, chloroform)
1
1
4
(
2
(
(
1
(
1
8
1
1
5
(
([a]~ +250 ° (c 0.51, chloroform) for (S)-(R)-3e [11]). ~H NMR (CDCI3): 8 1.15
(d, J 7 Hz, 3H), 1.74 (s, 6H), 3.72 (s, 3H), 3.76 (s, 3H), 3.78 (s, 6H), 3.45-4.38 (m,
8
H), 6.64-7.53 (m, 16H). 31P{~H} NMR (CDC13): 8 -27.0 (s), -21.1 (s). Anal.
Found: C, 67.44; H, 6.15; N, 1.89. C42H45NP2Fe talc.: C, 67.66; H, 6.08; N, 1.89%.
R)-(S)-4e: Yield 20%. Orange glassy solid, [a]~ -301 ° (c 0.51, chloroform). IH
NMR (CDC13): 8 1.27 (d, J 7 Hz, 3H), 1.77 (s, 6H), 3.74 (s, 3H), 3.81 (s, 3H), 3.93
s, 5H), 3.83-4.41 (m, 4H), 6.66-7.63 (m, 8H). 31p{1H} NMR (CDCI3): 8 -26.5
s). Anal. Found: C, 67.36; H, 6.53; N, 2.57. C2sH32NO2PFe talc.: C, 67.08; H,
.43; N, 2.79%.
R)-(S)-3f: Yield 27%. Orange glassy solid, [a]~ -258* (c 0.48, chloroform).
H NMR (250 MHz, CDC13): 8 1.05-1.15 (broad s, 3H), 1.76 (broad s, 6H), 2.15 (s,
(
(
(
6
(
1
6H), 2.21 (s, 6H), 2.23 (s, 6H), 2.27 (s, 6H), 3.66 (s, 3H), 3.70 (s, 3H), 3.71 (s, 6H),
3.6-4.4 (m, 8H), 6.80 (d, J 7 Hz, 2H), 6.92 (d, J 8 Hz, 2H), 6.95 (d, J 8 Hz, 2H),
7.23 (d, J 8 Hz, 2H). 31P{1H} NMR (CDCI3): 8 -24.9 (s), -19.6 (s). Anal.
Found: C, 70.00; H, 7.33; N, 1.79. CsoH6~O4NP2Fe cale.: C, 70.01; H, 7.17; N,
1.79%. (R)-(S)-4f: Yield 4%. Orange crystals (reerystallized from methanol), m.p.
146°C, [a]~ -286 ° (c 0.51, chloroform). IH NMR (CDC13): 8 1.26 (d, J 7 Hz,
3H), 1.78 (s, 6H), 2.16 (s, 6H), 2.29 (s, 6H), 3.66 (s, 3H), 3.73 (s, 3H), 3.92 (s, 5H),
3.8-4.4 (m, 4H), 6.81 (d, J 8 Hz, 2H), 7.25 (d, J 8 Hz, 2H). 31p{1H} NMR
(
CDC13): 8 -24.4 (s). Anal. Found: C, 68.94; H, 7.23; N, 2.51. C32H4oNO2PFe
talc.: C, 69.18; H, 7.39; N, 2.51%.
(
R)-I-[(S)-I ',2-Bis(diarylphosphino)ferrocenyl]ethyl acetates (5)
Preparation of (R)-(S)-5a (31p{1H} NMR (CDC13): 8 -25.5 (s), -17.9(s)) in
90% yield has been previously reported [8].