M. Yang et al. / Tetrahedron: Asymmetry xxx (2016) xxx–xxx
7
(m), 132.1 (s), 130.3 (d, J = 5.6 Hz), 128.8 (s), 128.6–127.9 (m),
127.0 (s), 126.7 (s), 60.7 (s), 59.6 (s), 55.6 (d, J = 11.7 Hz), 48.9 (d,
J = 5.4 Hz), 43.2 (s), 34.0 (s), 31.5 (d, J = 10.1 Hz), 24.8 (s), 22.6 (d,
J = 18.3 Hz), 22.1 (s), 21.9 (s), 21.0 (s), 15.2 (s). Calcd for
0.60 (d, J = 7.0 Hz, 3H), 0.42 (d, J = 6.8 Hz, 3H). 31P NMR
(162 MHz, CDCl3) d 35.63 (s). 13C NMR (101 MHz, CDCl3) d 145.2
(s), 137.0 (s), 132.4 (m, J = 18.8, 9.1 Hz), 130.2 (d, J = 3.8 Hz),
129.0 (s), 128.3 (d, J = 12.6 Hz), 127.8 (d, J = 2.3 Hz), 127.1 (s),
126.8 (s), 126.0 (d, J = 7.6 Hz), 104.4 (s), 103.9 (s), 102.7 (d,
J = 7.2 Hz), 77.5 (s), 64.0 (d, J = 1.7 Hz), 59.0 (s), 57.9 (s), 55.9 (d,
J = 13.3 Hz), 49.0(d, J = 5.7 Hz), 43.1 (s), 34.1 (s), 31.5 (s), 29.9 (s),
24.6 (s), 22.6 (s), 22.3 (s), 22.0 (s), 21.4 (s), 18.8 (s), 18.2 (d,
J = 13.7 Hz), 15.5 (s), 15.2 (s). Calcd for C31H39BrNO2P: C, 65.49;
H, 6.91. Found: C, 65.27; H, 6.84.
C31H39ClNO2P: C, 71.05; H, 7.50. Found: C, 70.86; H, 7.42.
4.7. (SP)- -Menthyl [(R)-1-phenylethylamino-m-bromophenyl
L
methyl]phenylphosphinate 3fA/3fB
White solid (307 mg, 54%, 81:19 drC), mp 166–168 °C; 1H NMR
(400 MHz, CDCl3) d 7.84–7.75 (m, 2H), 7.56 (t, J = 6.8 Hz, 1H), 7.52–
7.43 (m, 3H), 7.39 (dd, J = 13.1, 4.8 Hz, 2H), 7.30 (dd, J = 7.5, 3.7 Hz,
1H), 7.26 (s, 1H), 7.24–7.07 (m, 6H), 7.07–6.95 (m, 3H), 4.32 (dd,
J = 6.7, 4.2 Hz, 0.19H), 4.25–4.12 (m, 0.81H), 3.98 (d, J = 14.6 Hz,
0.81H), 3.73 (d, J = 18.1 Hz, 0.19H), 3.56–3.50 (m, 0.19H), 3.46 (q,
J = 6.4 Hz, 0.81H), 2.20 (s, 1H), 1.68–1.58 (m, 2H), 1.53 (d,
J = 11.6 Hz, 2H), 1.43 (s, 1H), 1.41–1.33 (m, 1H), 1.31 (d,
J = 6.6 Hz, 1H), 1.28–1.13 (m, 2H), 1.03 (t, J = 8.5 Hz, 3H), 0.99–
0.91 (m, 1H), 0.87 (ddd, J = 18.8, 10.6, 7.5 Hz, 2H), 0.79–0.63 (m,
8H), 0.50 (d, J = 6.9 Hz, 3H). 31P NMR (162 MHz, CDCl3) d 37.32 (s,
19%), 35.41 (s, 81%). 13C NMR (101 MHz, CDCl3) d 145.1 (s), 144
(s), 140 (d, J = 2.9 Hz), 138.6 (s), 133.1 (s), 133.0–131.8 (m), 131.5
(d, J = 5.1 Hz), 130.8–129.8 (m), 129.6 (m, J = 9.4, 2.2 Hz), 128.8
(s), 128.5 (s), 128.4–127.9 (m), 127.9–127.3 (m), 127.0 (d,
J = 12.4 Hz), 126.7 (s), 122.3 (s), 122.3 (s), 122.3 (s), 61.7 (s), 60.9
(s), 60.7 (s), 59.8 (s), 55.7 (d, J = 11.7 Hz), 55.3 (d, J = 14.5 Hz),
49.0 (dd, J = 17.6, 5.7 Hz), 43.2 (d, J = 10.8 Hz), 34.1 (d, J = 8.5 Hz),
31.5 (d, J = 11.9 Hz), 25.4 (s), 24.9 (d, J = 3.9 Hz), 22.8 (s), 22.5 (s),
22.4–22.3 (m), 22.0 (dd, J = 23.8, 21.3 Hz), 21.3 (s), 15.5 (s), 15.1
(s). Calcd for C31H39BrNO2P: C, 65.49; H, 6.91. Found: C, 65.23; H,
6.81.
4.10. (SP,S -C)-L-Menthyl [(R)-1-phenylethylamino-o-hydroxy
phenylmethyl]phenylphosphinate 3iA
a
White solid (243 mg, 48%, >99:1 drC), mp 194–198 °C; 1H NMR
(400 MHz, CDCl3) d 10.05 (s, 1H), 7.69 (dd, J = 11.2, 7.6 Hz, 2H), 7.56
(t, J = 7.4 Hz, 1H), 7.43 (td, J = 7.5, 3.5 Hz, 2H), 7.26 (s, 1H), 7.24–
7.17 (m, 2H), 7.17–7.04 (m, 3H), 6.83 (d, J = 8.1 Hz, 1H), 6.71 (dt,
J = 14.5, 7.3 Hz, 2H), 4.31 (dt, J = 15.1, 11.0 Hz, 1H), 4.15 (d,
J = 16.1 Hz, 1H), 3.56 (q, J = 6.6 Hz, 1H), 2.44 (s, 1H), 1.70 (dd,
J = 17.6, 10.4 Hz, 2H), 1.63–1.52 (m, 2H), 1.36–1.21 (m, 2H), 1.16
(d, J = 6.5 Hz, 3H), 1.05–0.83 (m, 3H), 0.71 (dd, J = 6.7, 2.8 Hz, 6H),
0.59 (d, J = 6.9 Hz, 3H). 31P NMR (162 MHz, CDCl3) d 40.36 (s). 13C
NMR (101 MHz, CDCl3) d 157.1 (d, J = 4.1 Hz), 144.3 (s), 132.7 (s),
132.6 (s), 132.5 (s), 131.1 (d, J = 7.1 Hz), 129.9 (s), 129.3 (s), 128.4
(s), 128.1 (d, J = 12.7 Hz), 127.2 (s), 126.6 (s), 120.8 (s), 119.5 (s),
118.8 (s), 62.2 (s), 61.1 (s), 55.5 (d, J = 12.8 Hz), 48.8 (d,
J = 5.3 Hz), 43.1 (s), 34.0 (s), 31.5 (s), 25.2 (s), 22.6 (s), 21.9 (s),
21.0 (s), 20.6 (s), 15.1 (s). Calcd for C31H40NO3P: C, 73.64; H, 7.97.
Found: C, 73.49; H, 7.88.
4.11. (SP)-L-Menthyl [(R)-1-phenylethylamino-2-methylpropyl]
phenylphosphinate 3jA/3jB
4.8.
(SP,S -C)-
L-Menthyl
[(R)-1-phenylethylamino-o-fluro
a
phenylmethyl]phenylphosphinate 3gA
White solid (260.0 mg, 57%, 85:15 drC), mp 194–198 °C; 1H
NMR (400 MHz, CDCl3) d 7.83 (dd, J = 23.6, 15.3 Hz, 2H), 7.60–
7.51 (m, 1H), 7.47 (dd, J = 13.1, 10.2 Hz, 2H), 7.23–7.11 (m, 3H),
6.98 (d, J = 6.2 Hz, 2H), 4.30–4.16 (m, 0.85H), 4.14 (d, J = 6.4 Hz,
0.15H), 3.52 (d, J = 6.3 Hz, 1H), 2.85 (d, J = 13.9 Hz, 1H), 2.37–2.11
(m, 2H), 1.92 (d, J = 6.5 Hz, 1H), 1.74–1.48 (m, 4H), 1.36 (t,
J = 10.0 Hz, 1H), 1.26 (dd, J = 21.4, 12.7 Hz, 2H), 1.10 (d, J = 6.4 Hz,
3H), 1.05–0.62 (m, 21H). 31P NMR (162 MHz, CDCl3) d 41.24 (s,
15%), 39.83 (s, 85%). 13C NMR (101 MHz, CDCl3) d 145.6 (s), 145.0
(d, J = 7.0 Hz), 135.4 (d, J = 5.6 Hz), 134.3 (d, J = 5.5 Hz), 133.9 (s),
133.1–131.9 (m), 131.9 (s), 128.8–127.9 (m), 127.7 (d, J = 3.5 Hz),
127.1 (s), 127.1 (s), 127.0 (s), 60.3–59.3 (m), 59.3–57.2 (m), 56.8–
56.4 (m), 56.4 (s), 49.4 (dd, J = 10.4, 4.8 Hz), 43.5 (s), 34.26 (s),
31.9–31.5 (m), 29.9 (s), 28.6 (t, J = 21.3 Hz), 28.3 (s), 25.7–24.6
(m), 24.6 (s), 24.3 (d, J = 8.8 Hz), 22.8 (t, J = 5.9 Hz), 22.6–21.9
(m), 21.9–21.5 (m), 21.4 (d, J = 3.7 Hz), 17.9–17.3 (m), 16.0–15.20
(m). Calcd for C28H42NO2P: C, 73.81; H, 9.29. Found: C, 73.62; H,
9.20.
White solid (284 mg, 56%, >99:1 drC), mp 175–178 °C; 1H NMR
(400 MHz, CDCl3) d 7.87 (dd, J = 11.2, 7.5 Hz, 2H), 7.56 (q, J = 6.8 Hz,
2H), 7.48 (td, J = 7.4, 3.3 Hz, 2H), 7.23 (dd, J = 13.0, 6.8 Hz, 1H),
7.19–7.10 (m, 4H), 7.01 (dd, J = 9.1, 3.3 Hz, 2H), 6.95 (d, J = 8.9 Hz,
1H), 4.55 (d, J = 15.4 Hz, 1H), 4.19–4.09 (m, 1H), 3.47 (q,
J = 6.6 Hz, 1H), 2.16 (br, 1H), 1.60 (d, J = 12.4 Hz, 1H), 1.50 (dd,
J = 10.1, 3.1 Hz, 2H), 1.25 (d, J = 5.5 Hz, 1H), 1.24–1.10 (m, 3H),
1.01 (d, J = 6.4 Hz, 3H), 0.94–0.80 (m, 2H), 0.67 (d, J = 6.5 Hz, 3H),
0.60 (d, J = 7.0 Hz, 3H), 0.42 (d, J = 6.8 Hz, 3H). 31P NMR
(162 MHz, CDCl3) d 35.61 (d, J = 4.9 Hz). 13C NMR (101 MHz, CDCl3)
d 162.5 (d, J = 6.3 Hz), 160.1 (d, J = 6.3 Hz), 145.4 (s), 133.7 (s),
132.4 (d, J = 9.5 Hz), 132.2 (d, J = 2.6 Hz), 130.0 (s), 129.1 (d,
J = 6.0 Hz), 128.5–127.7 (m), 127.1 (d, J = 4.5 Hz), 126.8 (s), 124.7
(d, J = 15.1 Hz), 124.4 (s), 115.1 (s), 114.8 (s), 55.8 (d, J = 12.8 Hz),
53.9–52.5 (m), 51.8 (d, J = 114.6 Hz), 48.9 (d, J = 5.6 Hz), 43.2 (s),
34.2 (s), 31.6 (s), 29.9 (s), 24.7 (s), 22.6 (s), 22.4–21.8 (m), 21.3
(d, J = 4.8 Hz), 15.3 (s). Calcd for C31H39FNO2P: C, 73.35; H, 7.74.
Found: C, 73.26; H, 7.65.
Acknowledgments
4.9.
(SP,S -C)-
L
-Menthyl
[(R)-1-phenylethylamino-o-bromo
a
The authors acknowledge the financial support of the Natural
Science Foundation of China (grant no. 20772055) and Natural
Science Foundation of Shandong Province (grant no.
ZR2014BP007).
phenylmethyl]phenylphosphinate 3hA
White solid (296 mg, 52%, >99:1 drC), mp 169–173 °C; 1H NMR
(400 MHz, CDCl3) d 7.87 (dd, J = 11.2, 7.5 Hz, 2H), 7.56 (q, J = 6.8 Hz,
2H), 7.48 (td, J = 7.4, 3.3 Hz, 2H), 7.23 (dd, J = 13.0, 6.8 Hz, 1H),
7.19–7.10 (m, 4H), 7.01 (dd, J = 9.1, 3.3 Hz, 2H), 6.95 (d, J = 8.9 Hz,
1H), 4.55 (d, J = 15.4 Hz, 1H), 4.19–4.09 (m, 1H), 3.47 (q,
J = 6.6 Hz, 1H), 2.16 (s, 1H), 1.60 (d, J = 12.4 Hz, 1H), 1.50 (dd,
J = 10.1, 3.1 Hz, 2H), 1.25 (d, J = 5.5 Hz, 1H), 1.24–1.10 (m, 3H),
1.01 (d, J = 6.4 Hz, 3H), 0.94–0.80 (m, 2H), 0.67 (d, J = 6.5 Hz, 3H),
Supplementary data
Supplementary data associated with this article can be found, in