B. Xiong et al. / Tetrahedron 70 (2014) 9057e9063
9061
128.6 (d, 1J (C,P)¼13.1 Hz; Ar), 127.6 (s; Ar), 122.7 (s; Ar), 65.7 (d, 1J
6.5 Hz; eCH2), 31.9 (s; eCH2); 31P NMR (160 MHz, CDCl3, 25 ꢀC):
¼31.4.
(C,P)¼4.0 Hz; eOCH2); 31P NMR (160 MHz, CDCl3, 25 ꢀC):
d¼32.6.
d
4.2.5. (Naphthalen-2-yl)methyl phenyl (phenyl) phosphinate
4.2.11. 3-Methylbut-2-enyl
(3k).12i Yield: 122.9 mg, (86%). Colorless oil. 1H NMR (400 MHz,
CDCl3, 25 ꢀC, TMS):
phenyl
(phenyl)
phosphinate
(3e). Yield: 150.4 mg, (84%). White solid, mp 117e119 ꢀC. 1H NMR
(400 MHz, CDCl3, 25 ꢀC, TMS):
d
¼7.76e7.88 (m, 7H; Ar), 7.41e7.48
d
¼7.80e7.85 (m, 4H; Ar), 7.42e7.52 (m, 6H; Ar),
(m, 8H; Ar), 5.21 (d, J¼6.8 Hz; 2H; eOCH2); 13C NMR (100 MHz,
5.39e5.43 (m, 1H; eCH]C(CH3)2), 4.54e4.57 (m, 2H; eOCH2), 1.71
CDCl3, 25 ꢀC, TMS):
d
¼133.7 (d, 1J (C,P)¼7.4 Hz; Ar), 133.1 (d, 1J
(s, 3H; eCH3), 1.59 (s, 3H, eCH3); 13C NMR (100 MHz, CDCl3, 25 ꢀC,
(C,P)¼2.2 Hz; Ar), 132.3 (d, 1J (C,P)¼2.7 Hz; Ar), 131.7 (d, 1J (C,P)¼
10.1 Hz; Ar), 131.3 (d, 1J (C,P)¼135.8 Hz; AreCeP), 128.7 (s; Ar),
128.5 (s; Ar), 128.4 (s; Ar), 128.0 (s; Ar), 127.7 (s; Ar), 127.0 (s; Ar),
126.3 (s; Ar), 126.3 (s; Ar), 125.6 (s; Ar), 66.5 (d, 1J (C,P)¼5.4 Hz;
TMS):
d
¼139.1 (s; Ar), 132.0 (d, 1J (C,P)¼2.8 Hz; Ar), 131.8 (d, 1J
(C,P)¼135.7 Hz; AreCeP), 131.7 (d, 1J (C,P)¼10.0 Hz; Ar), 128.4 (d, 1J
(C,P)¼13.0 Hz; eCH]C(CH3)2), 119.6 (d, 1J (C,P)¼6.9 Hz; eCH]
C(CH3)2), 61.6 (d, 1J (C,P)¼5.6 Hz; OCH2), 25.7 (s; eCH3), 18.0 (s;
eOCH2); 31P NMR (160 MHz, CDCl3, 25 ꢀC):
d
¼33.6. HRMS calcd for
eCH3); 31P NMR (160 MHz, CDCl3, 25 ꢀC):
d¼31.6.
C
23H19O2P: 358.1123, found: 358.1128.
4.2.12. 3-Chloropropyl phenyl (phenyl) phosphinate (3l).12j Yield:
4.2.6. Octyl phenyl (phenyl) phosphinate (3f).12d Yield: 153.4 mg,
133.7 mg, (91%). Colorless oil. 1H NMR (400 MHz, CDCl3, 25 ꢀC,
(93%). Colorless oil. 1H NMR (400 MHz, CDCl3, 25 ꢀC, TMS):
TMS):
d
¼7.79e7.84 (m, 4H; Ar), 7.51e7.55 (m, 2H; Ar), 7.43e7.48
d
¼7.79e7.85 (m, 4H; Ar), 7.49e7.54 (m, 2H; Ar), 7.42e7.47 (m, 4H;
(m, 4H; Ar), 4.16e4.21 (m, 2H; eOCH2), 3.40 (t, J¼6.4 Hz, 2H; eCH2),
13
Ar), 4.00e4.05 (m, 2H; OCH2e), 1.69e1.76 (m, 2H; eCH2), 1.26e1.41
(m, 10H; eCH2), 0.85e0.89 (m, 3H; CH3); 13C NMR (100 MHz, CDCl3,
2.14e2.20 (m, 2H; eCH2); C NMR (100 MHz, CDCl3, 25 ꢀC, TMS):
d
¼132.1 (d, 1J (C,P)¼2.1 Hz; Ar), 131.4 (d, 1J (C,P)¼10.1 Hz; Ar), 131.0
25 ꢀC, TMS):
d
¼132.0 (d, 1J (C,P)¼2.7 Hz; Ar), 131.7 (d, 1J (C,P)¼
(d, 1J (C,P)¼136.2 Hz; AreCeP), 128.4 (d, 1J (C,P)¼13.1 Hz; Ar), 61.4
(d, 1J (C,P)¼5.8 Hz; eOCH2), 40.8 (s; eCH2), 33.2 (d, 1J (C,P)¼5.4 Hz;
136.2 Hz; Ar), 131.6 (d, 1J (C,P)¼10.0 Hz; Ar), 128.5 (d, 1J (C,P)¼
13.0 Hz; Ar), 65.0 (d, 1J (C,P)¼6.0 Hz; OCH2e), 31.7 (s; eCH2), 30.5
(d, 1J (C,P)¼6.7 Hz; Ar), 29.7 (s; eCH2), 29.1 (d, 1J (C,P)¼5.1 Hz; Ar),
25.6 (s; eCH2), 22.6 (s; eCH2), 14.1 (s; eCH2); 31P NMR (160 MHz,
CH2); 31P NMR (160 MHz, CDCl3, 25 ꢀC):
d
¼33.2.
4.2.13. (Ethoxycarbonyl) (phenyl) methyl diphenyl phosphinate
CDCl3, 25 ꢀC):
d
¼32.2.
(3q). Yield: 100.7 mg, (53%). Yellow oil. 1H NMR (400 MHz, CDCl3,
25 ꢀC, TMS):
d
¼7.87e7.92 (m, 2H; Ar), 7.71e7.76 (m, 2H; Ar),
4.2.7. Methyl phenyl (phenyl) phosphinate (3g).12e Yield: 109.1 mg,
7.21e7.54 (m, 11H, Ar), 5.83 (d, J¼10.0 Hz,1H; eOCH), 4.06e4.16 (m,
(94%). Colorless oil. 1H NMR (400 MHz, CDCl3, 25 ꢀC, TMS):
2H; eOCH2), 1.13 (t, J¼6.8 Hz, 3H; eCH3); 13C NMR (100 MHz, CDCl3,
d
¼7.79e7.85 (m, 4H; Ar), 7.50e7.55 (m, 2H; Ar), 7.43e7.48 (m, 4H;
25 ꢀC, TMS):
d
¼169.0 (d, 1J (C,P)¼4.2 Hz; eC]O), 135.4 (d, 1J (C,P)¼
Ar), 3.77 (d, J¼7.2 Hz, 3H; OCH3); 13C NMR (100 MHz, CDCl3, 25 ꢀC,
4.8 Hz; Ar),132.3 (d,1J (C,P)¼2.8 Hz; Ar),131.8 (d,1J (C,P)¼2.6 Hz; Ar),
131.0 (d,1J (C,P)¼136.0 Hz; AreCeP),129.0 (s; Ar),128.6 (s; Ar),128.5
(d, 1J (C,P)¼7.4 Hz; Ar), 127.3 (s; Ar), 74.2 (d, 1J (C,P)¼5.0 Hz; eOCH),
61.7 (s; eOCH2), 13.9 (s; eCH3); 31P NMR (160 MHz, CDCl3, 25 ꢀC):
TMS):
d
¼132.2 (d, 1J (C,P)¼2.7 Hz; Ar),131.6 (d, 1J (C,P)¼10.0 Hz; Ar),
130.9 (d, 1J (C,P)¼136.5 Hz; AreCeP), 128.5 (d, 1J (C,P)¼13.1 Hz; Ar),
51.5 (d, 1J (C,P)¼5.9 Hz; OCH3); P NMR (160 MHz, CDCl3, 25 ꢀC):
31
d¼34.3.
d¼34.0. HRMS calcd for C22H21O4P: 380.1177, found: 380.1173.
4.2.8. Isopropyl phenyl (phenyl) phosphinate (3h).12f Yield:
4.2.14. 2-Methyl-benzyl diphenyl phosphinate (3r). Yield: 136.9 mg,
114.5 mg, (88%). Colorless oil. 1H NMR (400 MHz, CDCl3, 25 ꢀC,
(85%). Colorless oil. 1H NMR (400 MHz, CDCl3, 25 ꢀC, TMS):
TMS):
d
¼7.80e7.85 (m, 4H; Ar), 7.47e7.51 (m, 2H; Ar), 7.40e7.45
d
¼7.66e7.71 (m, 4H; Ar), 6.98e7.31 (m, 10H, Ar), 4.93 (d, J¼6.0 Hz,
13
(m, 4H; Ar), 4.64e4.70 (m, 1H; OCHe), 1.34 (d, J¼6.0 Hz, 6H; CH3);
2H; eOCH2), 2.15 (s, 3H; eCH3); C NMR (100 MHz, CDCl3, 25 ꢀC,
13C NMR (100 MHz, CDCl3, 25 ꢀC, TMS):
d
¼132.3 (d, 1J (C,P)¼
TMS):
d
¼136.7 (s; Ar), 134.3 (d, 1J (C,P)¼7.6 Hz; Ar), 132.2 (d, 1J
137.2 Hz; AreCeP), 131.9 (d, 1J (C,P)¼2.6 Hz; Ar), 131.5 (d, 1J (C,P)¼
10.0 Hz; Ar), 128.4 (d, 1J (C,P)¼13.0 Hz; Ar), 70.1 (d, 1J (C,P)¼5.9 Hz;
OCHe), 24.3 (d, 1J (C,P)¼4.1 Hz; CH3); 31P NMR (160 MHz, CDCl3,
(C,P)¼2.7 Hz; Ar), 131.6 (d, 1J (C,P)¼10.1 Hz; Ar), 131.4 (d, 1J (C,P)¼
135.7 Hz; AreCeP), 130.3 (s; Ar), 128.7 (s; Ar), 128.6 (s; Ar),128.5 (d,
1J (C,P)¼13.0 Hz; Ar), 126.0 (s; Ar), 64.6 (d, 1J (C,P)¼5.4 Hz; eOCH),
25 ꢀC):
d
¼30.8.
18.8 (s; eCH3); 31P NMR (160 MHz, CDCl3, 25 ꢀC):
d¼32.1. HRMS
calcd for C20H19O2P: 322.1123, found: 322.1121.
4.2.9. Butyl phenyl (phenyl) phosphinate (3i).12g Yield: 124.7 mg,
(91%). Colorless oil. 1H NMR (400 MHz, CDCl3, 25 ꢀC, TMS):
4.2.15. 4-Methoxybenzyl diphenyl phosphinate (3s). Yield: 87.9 mg,
d
¼7.79e7.84 (m, 4H; Ar), 7.50e7.54 (m, 2H; Ar), 7.42e7.47 (m, 4H;
(52%). Colorless oil. 1H NMR (400 MHz, CDCl3, 25 ꢀC, TMS):
Ar), 4.00e4.06 (m, 2H; OCH2), 1.68e1.75 (m, 2H, eCH2), 1.41e1.47
(m, 2H; eCH2), 0.92 (t, J¼7.2 Hz, 3H; CH3); 13C NMR (100 MHz,
d
¼7.71e7.76 (m, 4H; Ar), 7.39e7.43 (m, 2H; Ar), 7.31e7.35 (m, 4H;
Ar), 7.13e7.17 (m, 1H; Ar), 6.73e6.85 (m, 3H; Ar), 4.94 (d, J¼6.8 Hz,
CDCl3, 25 ꢀC, TMS):
d
¼132.0 (d, 1J (C,P)¼2.3 Hz; Ar), 131.6 (d, 1J
1H; eOCH2), 3.66 (s, 3H; eOCH3); 13C NMR (100 MHz, CDCl3, 25 ꢀC,
(C,P)¼136.4 Hz; AreCeP), 131.6 (d, 1J (C,P)¼10.0 Hz; Ar), 128.4 (d, 1J
(C,P)¼13.0 Hz; Ar), 64.6 (d, 1J (C,P)¼6.0 Hz; OCH2), 32.5 (d, 1J (C,P)¼
6.6 Hz; eCH2), 18.9 (s; eCH2), 13.6 (s; eCH3); 31P NMR (160 MHz,
TMS):
d
¼159.7 (s; Ar), 137.8 (d, 1J (C,P)¼7.4 Hz; Ar), 132.3 (d, 1J
(C,P)¼2.8 Hz; Ar), 131.7 (d, 1J (C,P)¼10.2 Hz; Ar), 131.3 (d, 1J (C,P)¼
135.9 Hz; AreCeP), 128.6 (d, 1J (C,P)¼13.1 Hz; Ar), 120.1 (s; Ar),
113.6 (d, 1J (C,P)¼7.4 Hz; Ar), 66.2 (d, 1J (C,P)¼5.5 Hz; eOCH), 55.2
CDCl3, 25 ꢀC):
d
¼32.2.
(s; eOCH3); 31P NMR (160 MHz, CDCl3, 25 ꢀC):
d
¼32.5. HRMS calcd
4.2.10. 3-Phenylpropyl phenyl (phenyl) phosphinate (3j).12h Yield:
for C20H19O3P: 338.1072, found: 338.1069.
163.1 mg, (97%). Colorless oil. 1H NMR (400 MHz, CDCl3, 25 ꢀC,
TMS):
d¼7.79e7.84 (m, 4H; Ar), 7.40e7.50 (m, 6H; Ar), 7.23e7.26
4.2.16. Benzyl dibutyl phosphate (4b).12k Yield: 127.7 mg, (85%).
Colorless oil. 1H NMR (400 MHz, CDCl3, 25 ꢀC, TMS):
(m, 2H; Ar), 7.14e7.17 (m, 3H; Ar), 4.03e4.10 (m, 2H; OCH2),
2.72e2.75 (m, 2H, eCH2), 1.41e1.47 (m, 2H; eCH2), 2.01e2.07 m,
d¼7.32e7.41
(m, 5H; Ar), 5.06 (d, J¼8.4 Hz, 2H; eOCH2), 3.98e4.04 (m, 4H;
eCH2), 1.59e1.66 (m, 4H; eCH2), 1.33e1.42 (m, 4H; eCH2), 0.91 (t,
J¼7.2 Hz, 6H; eCH3); 13C NMR (100 MHz, CDCl3, 25 ꢀC, TMS):
2H; eCH2); 13C NMR (100 MHz, CDCl3, 25 ꢀC, TMS):
d¼141.1 (s; Ar),
132.2 (d, 1J (C,P)¼2.7 Hz; Ar), 131.6 (d, 1J (C,P)¼136.1 Hz; AreCeP),
131.6 (d, 1J (C,P)¼10.1 Hz; Ar), 128.6 (s; Ar), 128.5 (s; Ar), 128.4 (s;
Ar), 126.0 (s; Ar), 64.2 (d, 1J (C,P)¼5.9 Hz; OCH2), 32.1 (d, 1J (C,P)¼
d
¼136.1 (d, 1J (C,P)¼6.8 Hz; Ar), 128.5 (s; Ar), 128.4 (s; Ar), 127.8 (s;
Ar), 68.9 (d, 1J (C,P)¼5.4 Hz; eOCH2), 67.5 (d, 1J (C,P)¼6.0 Hz; eCH2),