2300
S. K. Chakka et al. / Tetrahedron: Asymmetry 21 (2010) 2295–2301
(m, 4H), 1.90 (m, 1H), 0.91–0.24 (m, 6H); 13C NMR (100 MHz,
5.8.14. (S)-2-((S)-2-(Diphenylphosphino)-1,2,3,4-tetrahydro-
isoquinolin-3-yl)-4-phenyl-4,5-dihydrooxazole 18
CDCl3): d 171.2, 132.1, 131.9, 128.6, 128.5, 128.3, 127.1, 126.5,
126.0, 67.7, 63.4, 62.2, 45.2, 28.4, 19.3, 17.9; IR
m
max/cmꢃ1 (neat):
Yield: quant.; 1H NMR (400 MHz, C6D6): d 7.83–7.45 (m, 4H),
7.23–6.90 (m, 13H), 6.78–6.58 (m, 3H), 4.82–4.58 (m, 3H), 4.20
(d, J = 8.64 Hz, 1H), 3.88 (m, 1H), 3.56 (m, 1H), 3.31 (m, 1H), 3.08
(m, 1H); 31P NMR (162 MHz, C6D6): d 65.38.
3334, 2956, 1662, 1679, 1412, 1220, 1121, 1095, 737, 694; HR
ESI MS: m/z = 379.2016[M+H]+ (calcd for C23H27N2O3 379.2016).
5.8.9. (R)-4-Phenyl-2-((S)-1,2,3,4-tetrahydroisoquinolin-3-yl)-
4,5-dihydrooxazole 13
5.8.15. (R)-2-((S)-2-(Diphenylphosphino)-1,2,3,4-tetrahydro-
isoquinolin-3-yl)-4-isopropyl-4,5-dihydrooxazole 19
Yield: quant.; 1H NMR (400 MHz, C6D6): d 7.78 (m, 2H), 7.45 (m,
2H), 7.25–6.76 (m, 9H), 6.56 (m, 1H), 4.68–3.80 (m, 5H), 3.66–2.89
(m, 3H), 1.23 (m, 1H), 0.57 (d, J = 6.7 Hz, 3H), 0.50 (d, J = 6.7 Hz,
3H); 31P NMR (162 MHz, C6D6): d 67.99.
Rf = 0.3 (CH2Cl2/MeOH, 98:2); White solid (0.41 g, yield 59%);
mp: 129–131 °C (CH2Cl2); ½a D20
ꢂ
¼ þ46:15 (c 0.26, CH2Cl2); 1H
NMR (400 MHz, CDCl3): d 7.37–7.23 (m, 3H), 7.23–7.10 (m, 5H),
7.08–7.02 (m, 1H), 5.23 (t, J = 18.21 Hz, 1H), 4.68 (q, J = 10.10,
3.46 Hz, 1H), 4.16 (m, 3H), 3.92 (m, 1H), 3.19–3.06 (m, 2H), 1.93
(br s, 1H); 13C NMR (100 MHz, CDCl3): d 168.9, 142.0, 135.0,
133.3, 129.2, 128.7, 127.6, 126.5, 126.2, 126.1, 126.0, 75.0, 69.4,
5.8.16. (S)-2-((S)-2-(Diphenylphosphino)-1,2,3,4-tetrahydro-
isoquinolin-3-yl)-4-isopropyl-4,5-dihydrooxazole 20
Yield: quant.; 1H NMR (400 MHz, C6D6): d 7.76 (m, 2H), 7.44 (m,
2H), 7.21–6.79 (m, 9H), 6.57 (m, 1H), 4.63 (m, 1H), 4.41 (d, 16.4 Hz,
1H), 4.10 (d, 16.1 Hz, 1H), 3.64–3.01 (m, 6H), 1.27 (m, 1H), 0.64 (d,
J = 6.8 Hz, 3H), 0.54 (d, J = 6.8 Hz, 3H); 31P NMR (162 MHz, C6D6): d
68.39.
51.5, 47.6, 32.4. IR
m
max/cmꢃ1 (neat): 3225, 1663, 1493, 1454,
+
1366, 957, 916, 740, 697; HR ESI MS: m/z = 279.1500 [M+H]
(calcd for C18H19N2O 279.1492).
5.8.10. (S)-4-Phenyl-2-((S)-1,2,3,4-tetrahydroisoquinolin-3-yl)-
4,5-dihydrooxazole 14
5.8.17. Complex 21
Rf = 0.3 (CH2Cl2/MeOH, 98:2); Yellow oil (0.45, yield 65%);
Yield: 64%; ½a 2D0
ꢂ
¼ ꢃ3:1 (c 0.32, CH2Cl2); 1H NMR (400 MHz,
½
a 2D0
ꢂ
¼ ꢃ7:4 (c 1.85, CH2Cl2); 1H NMR (400 MHz, CDCl3): d 7.41–
CDCl3): d 7.81–7.58 (m, 10H), 7.56–7.41 (m, 7H), 7.40–7.11 (m,
11H), 6.82 (m, 2H), 6.71 (m, 1H), 5.21–4.72 (m, 2H), 4.38 (m,
1H), 4.11 (m, 2H), 3.76 (m, 2H), 3.36–3.18 (m, 3H), 2.76 (m, 1H),
2.31–2.06 (m, 2H), 1.98–1.78 (m, 8H); 13C NMR (100 MHz, CDCl3):
d 174.1, 163.1–160.7, 138.9, 135.0, 133.0–131.4 (m), 130.5–127.4
(m), 126.31, 125.6, 125.2, 123.8, 122.0, 117.6 (d, J = 3.89 Hz),
42.4, 36.2, 29.2, 20.1, 8.7; 31P NMR (162 MHz, CDCl3): d 66.13; IR
7.01 (m, 9H), 5.23 (t, J = 18.33 Hz, 1H), 4.68 (q, J = 10.04, 8.56 Hz,
1H), 4.20–4.13 (m, 3H), 3.92 (t, J = 5.84 Hz, 1H), 3.13 (d,
J = 9.08 Hz, 2H); 13C NMR (100 MHz, CDCl3) d 168.9, 142.1, 135.0,
133.4, 129.4, 129.0, 127.8, 126.8, 126.4, 126.2, 75.2, 69.5, 51.6,
47.7, 32.5; IR
916, 907, 749, 697; HR ESI MS: m/z = 279.1492[M+H]+ (calcd for
18H19N2O 279.1492).
m
max/cmꢃ1 (neat): 3227, 1663, 1493, 1109, 957,
C
m
max/cmꢃ1 (neat): 2928, 2034, 1610, 1353, 1273, 1115, 885, 838,
744, 711; HR ESI MS: m/z = 763.2418 [MꢃBArF]+ (calcd for
5.8.11. (R)-4-Isopropyl-2-((S)-1,2,3,4-tetrahydroisoquinolin-3-
yl)-4,5-dihydrooxazole (15)
C
38H39IrN2OP 763.2424).
Rf = 0.3 (CH2Cl2/MeOH, 9.8:0.2); Pale yellow oil (0.35 g, 54%);
5.8.18. Complex 22
Yield: 62%; ½a 2D0
ꢂ
¼ þ40:9 (c 1.15, CH2Cl2); 1H NMR (400 MHz,
½
a 2D0
ꢂ
¼ ꢃ12:7 (c 0.55, CH2Cl2); 1H NMR (400 MHz, CDCl3): d 7.18–
7.07 (m, 3H), 7.03 (m, 1H), 4.28 (q, J = 9.32, 8.12 Hz, 1H), 4.12 (s,
2H), 4.05–3.92 (m, 2H), 3.81–3.75 (m, 1H), 3.09–2.94 (m, 2H),
1.78 (m, 1H), 1.27 (t, J = 7.18 Hz, 1H), 0.96 (d, J = 6.88 Hz, 3H),
0.87 (t, J = 6.88 Hz, 3H); 13C NMR (100 MHz, CDCl3): d 167.6,
135.2, 133.6, 129.1, 126.2, 126.06, 126.04, 72.1, 70.4, 51.8, 48.0,
CDCl3): d 8.02–6.82 (m, 30H), 6.67 (m, 1H), 5.16–4.77 (m, 2H),
4.62 (m, 1H), 4.55–4.28 (m, 4H), 3.66 (m, 1H), 3.44–3.28 (m, 2H),
3.10–2.88 (m, 2H), 2.51–1.85 (m, 8H); 13C NMR (100 MHz, CDCl3):
d 174.7, 162.2 (q), 138.3, 135.2, 133.6–131.9 (m), 130.6–127.6 (m),
126.5, 126.4, 123.6, 120.9, 117.9 (t), 94.7, 69.1, 65.9, 63.9, 57.6,
53.9, 52.3, 36.5, 34.6, 30.1, 27.5, 22.8, 14.5; 31P NMR (162 MHz,
32.6, 18.9, 18.1; IR
m
max/cmꢃ1 (neat): 3298, 2960, 1717, 1642,
1525, 1222, 1065, 741, 615; HR ESI MS: m/z = 245.1468[M+H]+
CDCl3): d 65.83; IR
m
max/cmꢃ1 (neat): 2924, 2024, 1610, 1353,
(calcd for C15H21N2O 245.1462).
1272, 1114, 885, 734, 711, 681; HR ESI MS: m/z = 763.2424
[MꢃBArF]+ (calcd for C38H39IrN2OP 763.2424).
5.8.12. (S)-4-Isopropyl-2-((S)-1,2,3,4-tetrahydroisoquinolin-3-
yl)-4,5-dihydrooxazole 16
5.8.19. Complex 23
Yield: 68%; ½a 2D0
ꢂ
¼ þ1:6 (c 0.64, CH2Cl2); 1H NMR (400 MHz,
Rf = 0.3 (CH2Cl2/MeOH, 9.8:0.2); Pale yellow oil (0.38 g, yield
CDCl3): d 7.94–7.83 (m, 3H), 7.78–7.45 (m, 15H), 7.43–7.07 (m,
7H), 6.63 (d, 1H), 5.02–4.66 (m, 5H), 3.48–3.01 (m, 4H), 2.74 (m,
1H), 2.44–1.16 (m, 8H), 0.94–0.73 (m, 6H), 0.32 (d, J = 6.79 Hz,
3H); 13C NMR (100 MHz, CDCl3): d 173.4, 162.1 (q, J = 96.43,
44.72 Hz), 135.0–131.9 (m), 129.9–129.0 (m), 127.7–125.7 (m),
123.4, 120.7, 117.6, 94.7 (d), 92.8 (d), 73.3, 65.6 (t), 57.2, 53.6,
51.8, 42.4, 36.1, 35.4, 32.5, 29.1, 26.5; 31P NMR (162 MHz, CDCl3):
59%); ½a 2D0
ꢂ
¼ ꢃ10:9 (c 0.69, CH2Cl2); 1H NMR (400 MHz, CDCl3): d
7.19–7.08 (m, 3H), 7.02 (m, 1H), 4.33–4.14 (m, 2H), 4.11 (s, 2H),
4.05–3.91 (m, 2H), 3.79 (m, 1H), 3.02 (d, J = 7.58 Hz, 2H), 1.77 (m,
1H), 1.25 (t, J = 14.3 Hz, 1H), 0.96 (d, J = 6.79 Hz, 3H), 0.87 (d,
J = 6.79 Hz, 3H); 13C NMR (100 MHz, CDCl3): d 167.5, 135.1,
133.6, 129.4, 126.4, 126.2, 72.1, 70.4, 51.7, 47.8, 32.6, 32.5, 18.9,
18.1; IR
1069, 880, 736; HR ESI MS: m/z = 245.1468[M+H]+ (calcd for
15H21N2O 245.1462).
m
max/cmꢃ1 (neat): 3279, 2957, 1744, 1644, 1559, 1225,
d 65.5; IR m
max/cmꢃ1 (neat): 2924, 2036, 1610, 1353, 1272, 1114,
885, 744; HR ESI MS: m/z = 729.2580 [MꢃBArF]+ (calcd. for
C
C35H41IrN2OP 729.2580).
5.8.13. (R)-2-((S)-2-(Diphenylphosphino)-1,2,3,4-tetrahydro-
isoquinolin-3-yl)-4-phenyl-4,5-dihydrooxazole 17
5.8.20. Complex 24
Yield: 65%; ½a 2D0
ꢂ
¼ þ30:2 (c 0.86, CH2Cl2); 1H NMR (400 MHz,
Yield: quant.; 1H NMR (400 MHz, C6D6): d 7.85 (t, 2H), 7.54 (t,
2H), 7.21–6.84 (m, 13H), 6.71–6.61 (m, 2H), 4.82–4.56 (m, 3H),
4.20 (dd, J = 9.34, 2.99 Hz, 1H), 3.84 (m, 1H), 3.56 (m, 1H), 3.31
(m, 1H), 3.18 (m, 1H); 31P NMR (162 MHz, C6D6): d 65.81.
CDCl3): d 7.89–7.64 (m, 5H), 7.64–7.47 (m, 9H), 7.40–7.09 (m,
9H), 6.87–6.77 (m, 2H), 6.67 (d, J = 7.6 Hz, 1H), 5.04–4.62 (m,
5H), 3.46–3.19 (m, 4H), 2.80 (m, 1H), 2.01–1.62 (m, 8H), 1.61–
1.41 (m, 3H), 0.78 (d, J = 6.7 Hz, 3H), 0.17 (d, J = 6.7 Hz, 3H); 13C