T. Mino et al. / Tetrahedron: Asymmetry 12 (2001) 1677–1682
1681
Hz, 1H), 8.72 (d, J=8.3 Hz, 1H); 13C NMR (75 MHz,
CDCl3): l 24.53, 29.31, 52.84, 59.00, 65.08, 75.46, 122.74,
123.73, 125.74, 126.13, 126.59, 126.45, 128.43–134.64 (m,
Ar), 137.02, 138.40, 151.83; 31P NMR (121 MHz,
CDCl3): l 26.46; FAB-MS (m/z) 492 (M++H, 86);
HRMS (FAB) calcd for C32H31NO2P (M++H) 492.2092,
found 492.2072.
4.5.1. (R)-1-[2%-(Diphenylphosphino)phenyl]-2-(methoxy-
methyl)pyrrolidine (R)-1. Yield 87%; mp 60–62°C;
[h]2D0=+8.2 (c 1.00, CHCl3); 1H NMR (300 MHz,
CDCl3): l 1.54–1.86 (m, 3H), 2.01–2.16 (m, 1H), 2.63 (t,
J=8.9 Hz, 1H), 2.72 (q, J=7.1 Hz, 1H), 3.03 (dd, J=3.7
and 9.2 Hz, 1H), 3.12 (s, 3H), 3.45–3.56 (m, 1H),
3.63–3.77 (m, 1H), 6.81 (dq, J=1.3 and 3.8 Hz, 1H),
6.94 (t, J=7.4 Hz, 1H), 7.18–7.39 (m, 12H); 13C NMR
(75 MHz, CDCl3): l 24.48, 30.23, 56.03 (d, J=8.4 Hz),
59.27, 60.92 (d, J=2.5 Hz), 75.82, 121.62 (d, J=2.8 Hz),
123.92, 128.53–134.85 (m, Ar), 135.45 (d, J=10.9 Hz),
138.16 (d, J=12.6 Hz), 138.56 (d, J=11.9 Hz), 153.99
(d, J=19.6 Hz); 31P NMR (121 MHz, CDCl3): l −12.14;
FAB-MS (m/z) 376 (M++H, 64); HRMS (FAB) calcd
for C24H27NOP (M++H) 376.1830, found 376.1813.
4.3.4. (S)-1-[2%-(Diphenylphosphinyl)-1%-naphthalenyl]-2-
[(2¦-methoxyethoxy)methyl]pyrrolidine (S)-14. Yield
33%; mp 94–95°C; [h]2D5=+206 (c 1.0, CHCl3); 1H NMR
(300 MHz, CDCl3): l 1.43–1.90 (m, 3H), 2.17–2.24 (m,
2H), 2.84–3.29 (m, 7H), 3.24 (s, 3H), 4.29 (br, 1H), 7.17
(dd, J=8.6 and 12.6 Hz, 1H), 7.40–7.61 (m, 9H),
7.70–7.88 (m, 5H), 8.12 (br, 1H); 13C NMR (75 MHz,
CDCl3): l 24.67, 29.55, 54.04, 58.91, 63.45, 69.94, 71.73,
74.14, 125.94, 127.65, 128.14–135.49 (m, Ar), 137.04,
152.08; 31P NMR (121 MHz, CDCl3): l 26.61; FAB-MS
(m/z) 486 (M++H, 8); HRMS (FAB) calcd for
C30H33NO3P (M++H) 486.2198, found 486.2160.
4.5.2. (R)-1-[2%-(Diphenylphosphino)-1%-naphthalenyl]-2-
(methoxymethyl)pyrrolidine (R)-2. Yield 100%; mp 105–
106°C; [h]2D0=−12.3 (c 1.0, CHCl3); 1H NMR (300 MHz,
CDCl3): l 2.00 (br, 3H), 2.39 (br, 1H), 2.89 (br, 1H), 3.09
(s, 3H), 3.22 (br, 3H), 4.08 (br, 1H), 7.06 (br, 1H),
7.14–7.38 (m, 11H), 7.47 (br, 2H), 7.60 (d, J=8.5 Hz,
1H), 7.85 (br, 1H); 13C NMR (75 MHz, CDCl3): l 25.05,
30.11, 54.32, 58.59 (d, J=12.4 Hz), 63.09, 123.85,
124.85, 125.78–133.81 (m, Ar), 135.56, 138.55, 139.08;
31P NMR (121 MHz, CDCl3): l −16.22; FAB-MS (m/z)
426 (M++H, 57); HRMS (FAB) calcd for C28H29NOP
(M++H) 426.1987, found 426.1976.
4.4. Synthesis of (S)-1-[2%-(diphenylphosphinyl)-1%-naph-
thalenyl]-2-(hydroxymethyl)pyrrolidine (S)-16
To a solution of -prolinol (S)-15 (0.104 g, 1.03 mmol)
L
in THF (1 mL) at −80°C was added slowly n-BuLi in
hexane (1.56 M, 1.41 mL, 2.2 mmol) over 10 min, and
the mixture was stirred at rt for 2 h. Phosphine oxide 7
(0.359 g, 1.0 mmol) was added at 0°C and stirring was
continued for 20 h at rt. The mixture was diluted with
ether and quenched with satd NH4Cl. The organic layer
was washed with brine, dried over MgSO4, and concen-
trated under reduced pressure. The residue was purified
by silica-gel chromatography (elution with n-hexane/ace-
tone/EtOAc=10/4/1) (75%); mp 218–220°C; [h]2D5=
4.5.3. (S)-1-[2%-(Diphenylphosphino)-1%-naphthalenyl]-2-
[(2¦-methoxyethoxy)methyl]pyrrolidine (S)-3. Yield 85%;
mp 97–98°C; [h]2D5=+125 (c 1.00, CHCl3); 1H NMR (300
MHz, CDCl3): l 1.99–2.09 (m, 3H), 2.26–2.38 (m, 1H),
2.83 (br, 1H), 3.10–3.31 (m, 7H), 3.26 (s, 3H), 4.08 (br-s,
1H), 7.04 (br-s, 1H), 7.29 (br, 10H), 7.43–7.46 (m, 2H),
7.60 (d, J=8.5 Hz, 1H) 7.83 (br, 2H); 13C NMR (75
MHz, CDCl3): l 25.02, 30.19, 54.29, 58.94, 62.98, 70.12,
71.72, 75.07, 124.05, 125.74, 126.02–133.85 (m, Ar),
135.88, 138.50; 31P NMR (121 MHz, CDCl3): l −16.31;
FAB-MS (m/z) 470 (M++H, 0.4); HRMS (FAB) calcd
for C30H33NO2P (M++H) 470.2249, found 470.2210.
1
+12.5 (c 1.0, CHCl3); H NMR (300 MHz, CDCl3): l
1.59–1.85 (m, 4H), 2.12–2.19 (m, 2H), 3.00–3.08 (m, 1H),
3.30–3.39 (m, 1H), 3.63 (dd, J=4.5 and 12.3 Hz, 1H),
3.95 (br, 1H), 6.75–6.79 (br-m, 1H), 7.07 (dd, J=8.6 and
12.7 Hz, 1H), 7.41–7.72 (m, 10H), 7.79–7.86 (m, 2H),
7.93 (d, J=8.0 Hz, 1H), 7.97 (d, J=8.4 Hz, 1H); 13C
NMR (75 MHz, CDCl3): l 26.16, 28.17, 55.08, 63.24,
67.77, 124.77, 125.96, 126.35, 127.67, 128.23–132.34 (m,
Ar), 137.82, 153.50; 31P NMR (121 MHz, CDCl3): l
27.28; FAB-MS (m/z) 428 (M++H, 100); HRMS (FAB)
calcd for C27H27NO2P (M++H) 428.1779, found
428.1768.
4.5.4. (R)-1-[10%-(Diphenylphosphino)-9%-phenanthrenyl]-
2-(methoxymethyl)pyrrolidine (R)-5. Yield 66%; mp 70–
1
72°C; [h]2D5=−88 (c 0.25, CHCl3); H NMR (300 MHz,
CDCl3): l 1.99 (br, 1H), 2.12–2.21 (m, 2H), 2.39–2.48
(m, 1H), 2.96 (br-s, 3H), 3.09–3.25 (m, 2H), 3.55–3.73
(m, 2H), 4.05–4.17 (m, 1H), 7.01–7.06 (m, 1H), 7.08–7.54
(m, 11H), 7.55–7.76 (m, 3H), 7.85–8.34 (br-m, 2H), 8.64
(d, J=8.2 Hz, 1H); 13C NMR (75 MHz, CDCl3): l
24.09, 29.70, 55.58, 58.58, 64.98, 122.65, 125.61 (d,
J=9.4 Hz), 126.67, 127.12, 127.88, 128.15–133.17 (m,
Ar), 138.38; 31P NMR (121 MHz, CDCl3): l −17.97;
FAB-MS (m/z) 476 (M++H, 34); HRMS (FAB) calcd
for C32H29NO2P (M+−H) 474.1987, found 474.1955.
4.5. General procedure for reduction of aminophosphine
oxides
To a mixture of phosphine oxide (0.3 mmol), triethyl-
amine (0.34 mL, 1.2 mmol) and m-xylene (2 mL) was
added trichlorosilane (0.24 mL, 1.2 mmol) at 0°C under
an argon atmosphere. The reaction mixture was stirred
under reflux for 6 h. After being cooled to rt, the mixture
was diluted with ether and quenched with 2 M aq.
NaOH. The organic layer was washed with brine, dried
over MgSO4, and concentrated under reduced pressure.
The residue was purified by silica-gel chromatography
(elution with n-hexane/EtOAc=6/1).
4.5.5. (S)-1-[2%-(Diphenylphosphino)-1%-naphthalenyl]-2-
(hydroxymethyl)pyrrolidine (S)-17. Yield 66%; mp 183–
184°C; [h]2D5=+206 (c 1.0, CHCl3); 1H NMR (300 MHz,
CDCl3): l 1.87–1.96 (m, 2H), 2.20–2.27 (m, 2H), 2.37–
2.43 (m, 1H), 3.21 (q, J=8.0 Hz, 1H), 3.39 (t, J=11.8
Hz, 1H), 3.72 (d, J=12.0 Hz, 1H), 3.98 (t, J=5.9 Hz,
1H), 4.41 (dt, J=2.9 and 12.5 Hz, 1H), 7.00 (dd,