H. Suga et al.
Bull. Chem. Soc. Jpn., 76, No. 2 (2003) 333
H).
thyl-2,2ꢀ-diamine ((R)-BINIM-5ClOH): Orange plates (from
benzene-hexane); mp 165–166.5 °C; [α]D25 −360.5° (c 0.034,
CH2Cl2); 1H NMR (60 MHz, CDCl3) δ 6.55–8.21 (18H, m, Ar–H),
8.59 (2H, s, CHwN), 12.04 (2H, s, OH); IR (KBr) 3445 (OH),
1609 (CwN), 1559, 1478, 1277, 1179, 816, 747, 677 cm−1. Anal.
Calcd for C34H22Cl2N2O2: C, 72.73; H, 3.95; N, 4.99%. Found: C,
72.97; H, 4.00; N, 4.71%.
exo-2,5-Dimethyl-4-(2-oxo-1,3-oxazoline-3-carbonyl)-3-
phenylisoxazolidine (7b): Colorless viscous oil; [α]D20 −33.4°
(c 1.00, CHCl3); 31% ee estimated on the basis of HPLC (Daicel
Chiralcel OJ-R, methanol–water, 60:40 v/v, detector: UV 220 nm,
flow rate = 0.5 mL/min, tmajor = 27.0 min, tminor = 32.9 min). 1H
NMR (60 MHz, CDCl3) δ 1.37 (3H, d, J = 5.8 Hz, Me), 2.61 (3H,
s, N–Me), 2.93–5.15 (7H, m, CH, CH2), 7.32–7.82 (5H, m, Ph–
H).
(S)-N,Nꢀ-Bis(3,5-dibromo-2-hydroxybenzylidene)-1,1ꢀ-bi-
naphthyl-2,2ꢀ-diamine ((S)-BINIM-DBOH):
Orange plates
(R)-N,Nꢀ-Bis(2,6-dichlorobenzylidene)-1,1ꢀ-binaphthyl-2,2ꢀ-
diamine ((R)-BINIM-DC). A suspension of MS 4A (3.2 mm
pellets, 12.0 g), (R)-1,1ꢀ-binaphthyl-2,2ꢀ-diamine (0.602 g,
2.12 mmol), and 2,6-dichlorobenzaldehyde (0.742 g, 4.24 mmol)
in benzene (18mL) was stirred at room temperature for 16 h. Af-
ter the MS 4A was removed by filtration, the filtrate was concen-
trated in vacuo. The resulting solids were recrystallized from ben-
zene-hexane to give (R)-BINIM-DC (1.00 g, 79%): Yellow plate
(from benzene–hexane); mp 216–218 °C; [α]D24 −10.1° (c 0.96,
CH2Cl2); 1H NMR (270 MHz, C6D6) δ 6.17 (2H, t, J = 7.9 Hz, H-
4 of 2,6-Cl2C6H3), 6.60 (4H, d, J = 7.9 Hz, H-3 and H-5 of 2,6-
Cl2C6H3), 7.05–7.09 (2H, m, Ar-H), 7.19–7.22 (2H, m, Ar–H),
7.42 (2H, d, J = 8.6 Hz, Ar–H), 7.56 (2H, d, J = 8.3 Hz, Ar–H),
7.73 (2H, d, J = 7.9 Hz, Ar–H), 7.81 (2H, d, J = 8.6 Hz, Ar–H),
8.69 (2H, s, CHwN); IR (KBr) 3051, 1636, 1615 (CwN), 1577,
1429, 814, 777, 748 cm−1. Anal. Calcd for C34H20Cl4N2: C, 68.2;
H, 3.37; N, 4.68%. Found: C, 68.4; H, 3.52; N, 4.60%.
BINIM-OH, BINIM-DCOH, BINIM-3ClOH, BINIM-
5ClOH, BINIM-3OMeOH, and BINIM-DBOH were prepared
according to a procedure reported by Stack.9 A solution of 1,1ꢀ-bi-
naphthyl-2,2ꢀ-diamine (0.100 g, 0.70 mmol) and the correspond-
ing salicylaldehyde derivative (0.35 mmol) in ethanol (3.0 mL)
was heated under reflux for 6 h. The resulting crystals were fil-
tered and then recrystallized from benzene–hexane. Yields:
BINIM-OH, 88%; BINIM-DCOH, 80%; BINIM-3ClOH, 69%;
BINIM-5ClOH, 63%; BINIM-3OMeOH, 65%; BINIM-DBOH,
88%.
(from benzene-hexane); mp 183–185 °C; [α]D25 +398.7° (c 1.03,
CH2Cl2); 1H NMR (60 MHz, CDCl3) δ 7.25–8.19 (16H, m, Ar–H),
8.50 (2H, s, CHwN), 12.91 (2H, s, OH); IR (KBr) 3439 (OH),
1603 (CwN), 1588, 1549, 1443, 1202, 1163, 812 cm−1. Anal. Cal-
cd for C34H20Br2N2O2: C, 50.53; H, 2.49; N, 3.47%. Found: C,
50.80; H, 2.55; N, 3.24%.
(R)-N,Nꢀ-Bis(2-hydroxy-3-methoxybenzylidene)-1,1ꢀ-bi-
naphthyl-2,2ꢀ-diamine ((R)-BINIM-3OMeOH):
Orange
plates (from benzene–hexane); mp 274–275 °C; [α]D25 −364.5°
1
(c 0.030, CH2Cl2); H NMR (60 MHz, CDCl3) δ 3.76 (6H, s,
OMe), 6.78–8.13 (18H, m, Ar–H), 8.59 (2H, s, CHwN), 12.31
(2H, s, OH); IR (KBr) 3439 (OH), 1607 (CwN), 1589, 1574, 1460,
1400, 1252, 1204, 970 cm−1. Anal. Calcd for C36H28N2O4: C,
78.24; H, 5.11; N, 5.07%. Found: C, 78.54; H, 5.00; N, 4.88%.
BINIM-DTBOH was prepared according to the procedure re-
ported by Evans.10
(S)-N,Nꢀ-Bis(3,5-di-t-butyl-2-hydroxybenzylidene)-1,1ꢀ-bi-
naphthyl-2,2ꢀ-diamine ((S)-BINIM-DTBOH): Orange plates
(from benzene–hexane); mp 112–114 °C; [α]D25 +433.9° (c 1.01,
CH2Cl2); 1H NMR (60 MHz, CDCl3) δ 1.22 (18H, s, t-Bu), 7.02–
8.13 (16H, m, Ar–H), 8.66 (2H, s, CHwN), 12.72 (2H, s, OH); IR
(KBr) 3451 (OH), 2957, 2907, 2870, 1613 (CwN), 1582, 1466,
1359, 1248, 818 cm−1. Anal. Calcd for C50H56N2O2: C, 83.76; H,
7.87; N, 3.91%. Found: C, 83.83; H, 8.11; N, 3.62%.
References
(S)-N,Nꢀ-Bis(2-hydroxybenzylidene)-1,1ꢀ-binaphthyl-2,2ꢀ-
diamine ((S)-BINIM-OH): Yellow plates (from benzene-hex-
ane); mp 255–256.5 °C; [α]D25 +382.9° (c 0.16, CH2Cl2); 1H NMR
(60 MHz, CDCl3) δ 6.63–8.19 (20H, m, Ar–H), 8.66 (2H, s,
CHwN), 12.08 (2H, s, OH); IR (KBr) 3440 (OH), 3053, 1609
(CwN), 1568, 1493, 1462, 1283, 1196, 818 cm−1. Anal. Calcd for
C34H24N2O2: C, 82.91; H, 4.91; N, 5.69%. Found: C, 83.18; H,
4.82; N, 5.41%.
1
a) J. J. Tufariello, in “1,3-Dipolar Cycloaddition
Chemistry,” ed. by A. Padwa, John Wiley & Sons, New York
(1984), Vol. 2, p. 83. b) E. Breuer, H. G. Aurich, and A. Nielsen,
“Nitrones, nitronates and nitroxides,” John Wiley & Sons,
Chichester (1989). c) K. B. G. Torssell, “Nitrile Oxides, Nitrones
and Nitronates in Organic Synthesis,” VCH, New York (1988). d)
K. V. Gothelf and K. A. Jørgensen, Chem. Rev., 98, 863 (1998).
2
(1997).
3
For a review: M. Frederickson, Tetrahedron, 53, 403
(S)-N,Nꢀ-Bis(3,5-dichloro-2-hydroxybenzylidene)-1,1ꢀ-bi-
naphthyl-2,2ꢀ-diamine ((S)-BINIM-DCOH):
Orange plates
a) S. Murahashi, Y. Imada, M. Kohno, and T. Kawakami,
(from benzene-hexane); mp 189–191 °C; [α]D25 +471.8° (c 0.50,
CH2Cl2); 1H NMR (60 MHz, CDCl3) δ 7.10–8.19 (16H, m, Ar–H),
8.55 (2H, s, CHwN), 12.74 (2H, s, OH); IR (KBr) 3409 (OH),
1605 (CwN), 1557, 1449, 1202, 1179, 868, 737 cm−1. Anal. Calcd
for C34H20Cl4N2O2: C, 64.78; H, 3.20; N, 4.44%. Found: C,
64.94; H, 3.37; N, 4.21%.
Synlett, 1993, 395. b) K. V. Gothelf and K. A. Jørgensen, J. Org.
Chem., 59, 5687 (1994). c) K. V. Gothelf, I. Thomsen, and K. A.
Jørgensen, J. Am. Chem. Soc., 118, 59 (1996). d) K. V. Gothelf, R.
G. Hazell, and K. A. Jørgensen, J. Org. Chem., 61, 346 (1996).
e) K. B. Jensen, K. V. Gothelf, R. G. Hazell, and K. A. Jørgensen,
J. Org. Chem., 62, 2471 (1997). f) K. V. Gothelf and K. A.
Jørgensen, Acta Chem. Scand., 50, 652 (1996). g) K. B. Jensen,
K. V. Gothelf, and K. A. Jørgensen, Helv. Chim. Acta, 80, 2039
(1997). h) K. V. Gothelf, R. G. Hazell, and K. A. Jørgensen, J.
Org. Chem., 63, 5483 (1998). i) S. Kobayashi, R. Akiyama, M.
Kawamura, and H. Ishitani, Chem. Lett., 1997, 1039. j) S.
Kobayashi and M. Kawamura, J. Am. Chem. Soc., 120, 5840
(1998). k) K. Hori, H. Kodama, T. Ohta, and I. Furukawa, Tetra-
hedron Lett., 37, 5947 (1996). l) K. Hori, J. Ito, T. Ohta, and T.
Furukawa, Tetrahedron, 54, 12737 (1998). m) K. Hori, H.
(R)-N,Nꢀ-Bis(3-chloro-2-hydroxybenzylidene)-1,1ꢀ-binaph-
thyl-2,2ꢀ-diamine ((R)-BINIM-3ClOH): Orange plates (from
benzene-hexane); mp 230–230.5 °C; [α]D25 = −458.2° (c 0.32,
CH2Cl2); 1H NMR (60 MHz, CDCl3) δ 6.57–8.17 (18H, m, Ar–H),
8.60 (2H, s, CHwN), 12.77 (2H, s, OH); IR (KBr) 3436 (OH),
1644, 1615 (CwN), 1481, 1447, 1383, 1362, 1298, 1221, 833 cm−1
.
Anal. Calcd for C34H22Cl2N2O2: C, 72.73; H, 3.95; N, 4.99%.
Found: C, 72.59; H, 4.21; N, 4.71%.
(R)-N,Nꢀ-Bis(5-chloro-2-hydroxybenzylidene)-1,1ꢀ-binaph-