H. Suga et al.
2H, bs), 3.68–3.78 (1H, m), 3.99–4.15 (3H, m), 4.30–4.41 (2H,
Bull. Chem. Soc. Jpn., 77, No. 3 (2004)
567
(
1.1 mmol), and 2-quinolinecarbaldehyde (0.742 g, 4.24 mmol) was
heated under reflux in benzene (9.0 mL) for 4 h. After the MS 4A
was removed by filtration, the filtrate was concentrated in vacuo.
The resulting solids were recrystallized from diethyl ether to give
m), 5.72 (1H, dd, J ¼ 5:6, 3.0 Hz), 6.21 (1H, dd, J ¼ 5:6, 3.0
Hz), 7.20 (5H, s).
(
1R,2R,3S,4S)-3-(3-Ethoxycarbonylbicyclo[2.2.1]hept-5-en-
-ylcarbonyl)-2-oxazolidinone (3d):11a,12 A mixture of 78:22
ꢃ
2
(R)-BINIM-2QN (0.278 g, 49%): Yellow plates; mp 125.5–129 C
25
2
5
ꢃ
ꢃ
endo- and exo-isomers; Colorless oil; ½ꢀꢅ þ159:45 (c 0.98,
(diethyl ether); ½ꢀꢅ þ34:50 (c 1.00, CH2Cl2); IR (KBr) 1614
D
D
ꢂ1
CHCl3); 96% ee estimated on the basis of HPLC using a chiral col-
umn (Daicel Chiralpak AD with hexane–2-PrOH, 39:1 v/v, detec-
(C=N), 1591, 1558, 1502, 1425, 1203, 1111, 968, 895 cm
;
1
H NMR (60 MHz, CDCl3) ꢁ 7.26–8.13 (24H, m, Ar-H), 8.65
(2H, s, CH=N); HRMS (EI) m=z 562.2134. Calcd for C40H26N4:
M, 562.2156. Anal. Calcd for C40H26N4: C, 85.38; H, 4.66; N,
9.96%. Found: C, 85.22; H, 4.90; N, 9.76%.
ꢃ
tor: UV 220 nm, flow rate = 0.5 mL/min, 35 C, exominor: tR ¼
9
5:5 min, endomajor: tR ¼ 106:6 min, exomajor: tR ¼ 114:3 min,
endominor: tR ¼ 123:2 min), IR (neat) 2984, 1778 (C=O), 1726
0
0
0
(
C=O), 1695 (C=O), 1386, 1365, 1325, 1280, 1221, 1114, 1037,
(S)-N,N -Bis[2-(benzyloxy)benzylidene]-1,1 -binaphthyl-2,2 -
diamine ((S)-BINIM-OBn): Pale-yellow powder; mp 173–174
ꢂ1
1
435, 408 cm ; H NMR (CDCl3, 60 MHz) ꢁ 1.23 (3H ꢄ 22/
100, t, J ¼ 7:1 Hz, exo), 1.26 (3H ꢄ 78/100, t, J ¼ 7:1 Hz, endo),
1.42–1.69 (2H, m), 2.90 (1H, dd, J ¼ 1:7, 4.6 Hz), 3.24 (1H, bs),
3.46 (1H, bs), 3.67–5.32 (7H, m), 5.72 (1H, dd, J ¼ 5:6, 2.9 Hz),
6.21 (1H, dd, J ¼ 5:6, 2.9 Hz).
ꢃ
26
D
ꢃ
C (benzene–hexane); ½ꢀꢅ ꢂ1:52 (c 1.01, CH2Cl2); IR (KBr)
1610 (C=N), 1487, 1452, 1373, 1294, 1246, 1224, 1159, 1105,
ꢂ1
1
1016, 972, 812, 750, 696 cm
; H NMR (60 MHz, CDCl3) ꢁ
4.92 (4H, s, CH2), 6.70–8.00 (30H, m, Ar-H), 8.81 (2H, s,
CH=N); HRMS (EI) m=z 672.2813. Calcd for C48H36N2O2: M,
672.2775. Anal. Calcd for C48H36N2O2: C, 85.69; H, 5.39; N,
4.16%. Found: C, 85.71; H, 5.38; N, 4.15%.
(
1R,2R,4R)-2-(Bicyclo[2.2.1]hept-5-en-2-ylcarbonyl)-4,4-di-
methyl-1-(1-naphthylmethyl)-3-pyrazolidinone (3e): Colorless
26
ꢃ
ꢃ
solid; mp 143–144 C; ½ꢀꢅ þ80:52 (c 1.00, CHCl3); 94% ee es-
D
0
0
0
timated on the basis of HPLC using a chiral column (Daicel Chir-
alpak AD with hexane–2-PrOH, 39:1 v/v, detector: UV 254 nm,
(R)-N,N -Bis(8-quinolylmethylene)-1,1 -binaphthyl-2,2 -di-
ꢃ
amine ((R)-BINIM-8QN): Yellow plates; mp 220–225.5 C (di-
ꢃ
24
chloromethane–hexane); ½ꢀꢅ þ442:45ꢃ (c 1.00, CH2Cl2); IR
flow rate = 0.5 mL/min, 17 C, endominor: tR ¼ 35:3 min,
D
endomajor: tR ¼ 39:4 min), IR (KBr) 2978, 2945, 1768 (C=O),
(KBr) 3051, 2953, 2924, 1616 (C=N), 1591, 1570, 1317, 1201,
ꢂ1
1
1
cm
684 (C=O), 1350, 1336, 1300, 1211, 1182, 798, 779, 692
891 cm ; H NMR (60 MHz, CDCl3) ꢁ 7.00–8.45 (24H, m, Ar-
H), 8.58 (2H, s, CH=N); HRMS (EI) m=z 562.2138. Calcd for
C40H26N4: M, 562.2156. Anal. Calcd for C40H26N4: C, 85.38; H,
4.66; N, 9.96%. Found: C, 85.59; H, 4.83; N, 9.68%.
ꢂ1
1
; H NMR (CDCl3, 400 MHz) ꢁ 1.02–1.60 (4H, m), 1.29
(
(
6H, s), 2.69–2.81 (3H, m), 2.96 (1H, bs), 3.44 (1H, bs), 4.40
1H, d, J ¼ 13:4 Hz), 4.52 (1H, d, J ¼ 13:4 Hz), 5.67 (1H, dd,
0
0
0
J ¼ 5:6, 2.7 Hz), 6.07 (1H, dd, J ¼ 5:6, 2.7 Hz), 7.25–8.22 (7H,
m); HRMS m=z 374.2009. Calcd for C24H26N2O2: M, 374.1996.
Anal. Calcd for C24H26N2O2: C, 76.98; H, 7.00; N, 7.48%. Found:
C, 76.93; H, 7.15; N, 7.38%.
(R)-N,N -Bis(2-naphthylmethylene)-1,1 -binaphthyl-2,2 -di-
amine ((R)-BINIM-2NAP): Pale-yellow plates; mp 113–115.5
ꢃ
25
C (benzene–hexane); ½ꢀꢅ þ255:09ꢃ (c 1.01, CH2Cl2); IR
D
(KBr) 3053, 2955, 2954, 1614 (C=N), 1502, 1120, 970, 825,
ꢂ1
1
3
-[(1R)-4-Methyl-3-cyclohexenylcarbonyl]-2-oxazolidinone
26
752 cm ; H NMR (60 MHz, CDCl3) ꢁ 7.12–8.05 (26H, m, Ar-
H), 8.28 (2H, s, CH=N); HRMS (EI) m=z 560.2250. Calcd for
C42H28N2: M, 560.2251. Anal. Calcd for C40H28N2: C, 89.97; H,
5.03; N, 5.00%. Found: C, 89.65; H, 5.75; N, 4.61%.
1
1a,11b,12
ꢃ
ꢃ
(
CHCl3); 49% ee determined by HPLC after conversion to the cor-
4):
Colorless solid; mp 66–67 C; ½ꢀꢅ þ19:34 (c 0.38,
D
1
1b
responding (R)-ꢀ-methylbenzyl amide (Daicel Chiralpak AS
with hexane–2-PrOH, 19:1 v/v, detector: UV 254 nm, flow rate
= 0.5 mL/min, 35 C, minor: tR ¼ 27:1 min, major: tR ¼ 30:0
min); IR (KBr) 2922, 1782 (C=O), 1693 (C=O), 1392, 1367,
336, 1259, 1228, 1211, 1043, 758, 707 cm ; H MNR (CDCl3,
00 MHz) ꢁ 1.64–2.26 (6H, m), 1.68 (3H, s), 3.66 (1H, m), 4.03
0
0
0
(R)-N,N -Bis(1-naphthylmethylene)-1,1 -binaphthyl-2,2 -di-
ꢃ
ꢃ
amine ((R)-BINIM-1NAP): Pale-yellow plates; mp 56.0–63.0 C
25
(benzene–hexane); ½ꢀꢅ þ105:82ꢃ (c 1.00, CH2Cl2); IR (KBr)
D
ꢂ1
1
ꢂ1
1
4
1631, 1608 (C=N), 1587, 1504, 1205, 817, 802, 773, 746 cm
;
1
H NMR (60 MHz, CDCl3) ꢁ 6.98–8.23 (26H, m, Ar-H), 8.83
(2H, s, CH=N); HRMS (EI) m=z 560.2251. Calcd for C42H28N2:
M, 560.2251. Anal. Calcd for C40H28N2: C, 89.97; H, 5.03; N,
5.00%. Found: C, 89.49; H, 5.42; N, 4.71%.
(
2H, t, J ¼ 8:3 Hz), 4.00 (2H, t, J ¼ 8:3 Hz), 5.40 (1H, bs).
-[(1R,2S)-2-Acetoxy-3-cyclohexenylcarbonyl]-2-oxazolidi-
3
none (5):
1
1b
A mixture of 80:20 cis- and trans-isomers; Colorless
26
ꢃ
ꢃ
solid; mp 74–75 C; ½ꢀꢅ þ66:75 (c 0.20, CHCl3); 38% ee (cis)
2-Acryloyl-4,4-dimethyl-1-(1-naphthylmethyl)-3-pyrazolidi-
none (2e):10 To a solution of acrylic acid (1.44 g, 1.36 mL, 20.0
D
and 34% ee (trans) estimated on the basis of HPLC using a chiral
column (Daicel Chiralcel OD-H with hexane–2-PrOH, 4:1 v/v, de-
ꢃ
mmol) in ethyl acetate (100 mL) at 0 C was first added triethyl-
amine (2.02 g, 2.80 mL, 20.0 mmol), followed by acryloyl chloride
(1.81 g, 1.62 mL, 20 mmol) over a period of 2 min. The reaction
ꢃ
tector: UV 220 nm, flow rate = 1.0 mL/min, 35 C, cismajor: tR ¼
8
:9 min, cisminor: tR ¼ 12:2 min, transmajor: tR ¼ 15:4 min,
ꢃ
transminor: tR ¼ 17:8 min), IR (KBr) 2939, 1778 (C=O), 1739
mixture was stirred at 0 C for 40 min, and then at room temper-
(
1
C=O), 1693 (C=O), 1487, 1437, 1392, 1369, 1313, 1224, 1120,
ꢂ1
ature for 30 min. After the mixture was filtered through filter paper,
the filter cake was washed with ethyl acetate. The filtrate was con-
centrated in vacuo. The residue was taken up in hexane (40 mL)
and swirled, then filtered and concentrated in vacuo again. The an-
hydride was dissolved in THF (14 mL) and immediately used in the
following step. To a suspension of 4,4-dimethyl-1-(1-naphthyl-
methyl)-3-pyrazolidinone10a (2.54 g, 10.0 mmol) and LiCl (0.85
g, 20 mmol) in THF (15 mL) was added triethylamine (2.02 g,
2.80 mL, 20.0 mmol), followed by the anhydride solution prepared
above by the use of a cannula. The resulting slurry was stirred at
room temperature for 4 h. After removal of the solvent, 40 mL
of a 1 mol/L HCl solution was added and extracted with CH2Cl2
1
095, 1032, 999, 985, 964, 916, 887, 761, 711, 684 cm ; H NMR
(
(
CDCl3, 60 MHz) ꢁ 1.62–2.24 (4H, m), 1.95 (3H, s), 3.73–4.59
5H, m), 5.68–6.02 (3H, m).
BINIM-DC, BINIM-OH, BINIM-DCOH, BINIM-3ClOH,
BINIM-5ClOH, BINIM-DBOH, BINIM-3OMeOH, BINIM-
MeOH, BINIM-DTBOH, and BINIM-OBn were prepared
5
according to the procedures reported previously.
6
A General Procedure for Preparation of the Other BINIMs
0
0
was Exemplified by the Reaction of (R)-1,1 -Binaphthyl-2,2 -di-
amine with 2-Quinolinecarbaldehyde. A suspension of MS 4A
0
0
(
3.2 mm pellets, 6.0 g), (R)-1,1 -binaphthyl-2,2 -diamine (0.300 g,