P. Bałczewski et al. / Tetrahedron: Asymmetry 17 (2006) 1209–1216
1215
0
C3 H); 13C NMR (125 MHz, CDCl3) d = 11.21 (d, 1JC–P
=
127.11, 127.20, 128.68, 128.71, 129.11, 129.16 (C–Ph),
0
145.7 Hz, C1H3), 11.39 (d, JC–P = 146.8 Hz, C1 H3),
169.58 (d, JC–P = 4.3 Hz, C4), 169.75 (d, JC–P = 4.4 Hz,
1
3
3
0
19.05 (d, JC–P = 5.3 Hz, C6H3), 19.35 (d, JC–P = 5.1 Hz,
C4 ); IR (film): m/cmꢀ1 3007, 2955, 1757, 1496, 1437,
1222, 1065, 1039, 989, 924, 730; MS-CI (isobutane): m/z
(%) 259 (M++1, 100); MS-HR-CI: M++1, found:
259.0737 for C11H16O5P—calculated 259.0735.
3
3
0
C6 H3), 51.030 (d, JC–P = 6.8 Hz, C2H3), 52.17 (d, JC–P
=
3
3
0
6.8 Hz, C2 H3), 52.29, 52.32 (2 · s, C5H3, C5 H3), 69.86
0
(d, JC–P = 6.2 Hz, C3H), 70.27 (d, JC–P = 5.8 Hz, C3 H),
2
2
171.32 (d, JC–P = 3.4 Hz, C4), 171.44 (d, JC–P = 3.5 Hz,
3
3
0
C4 ); IR (film): m/cmꢀ1 2995, 2848, 1744, 1316, 1217,
1101, 1053, 1001, 900; MS-CI (isobutane): m/z (%) 197
(M++1, 100); MS-HR-CI: M++1, found: 197.0578 for
C6H14O5P—calculated 197.0573.
4.6.4. Methyl 2-(methoxy(methyl)phosphoryloxy)-2-methyl-
propanoate 6d.
2
O
P
1
Me
OMe O
5
4.6.2. (SC,RP+SP)-Methyl 2-(methoxy(methyl)phosphoryl-
oxy)-2-phenylacetate 6b.
O
3
4
OMe
Me Me
6
6'
2, 2'
OMe O
3, 3'
4, 4' OMe
H Ph
O
P
1, 1'
Me
Yield: 65%; a colourless liquid; 31P NMR (81 MHz,
5, 5'
O
CDCl3): d = 31.8 ppm; 1H NMR (500 MHz, CDCl3):
2
d = 1.50 (d, 3H, JH–P = 18.0 Hz, C1H3), 1.58, 1.65,
0
3
(2 · s, 6H, C6H3, C6 H3), 3.67 (d, 3H, JH–P = 11.3 Hz,
25
C2H3), 3.73 (s, 3H, C5H3); 13C NMR (125 MHz, CDCl3):
Yield: 63%; a colourless liquid; ½aꢂ589 ¼ þ91:2 (c 2.0,
CHCl3); 31P NMR (81 MHz, CDCl3): d = 33.85,
d = 13.12 (d, JC–P = 148.3 Hz, C1H3), 26.84, 26.90 (2 · s,
1
0
1
C6H3, C6 H3), 51.35 (d, JC–P = 6.5 Hz, C2H3), 52.42 (s,
C5), 80.41 (s, C3), 173.20 (s, C4); IR (film): m/cmꢀ1 2994,
2955, 1748, 1250, 1144, 1052, 1021, 809; MS-CI (iso-
butane): m/z (%) = 211 (M++1, 100); MS-HR-CI: M++1,
found: 211.0735 for C7H16O5P—calculated 211.0728.
2
33.73 ppm, (1:0.8); H NMR (500 MHz CDCl3): d = 1.32
2
2
(d, 3H, JH–P = 17.4 Hz, C1H3), 1.61 (d, 3H, JH–P
=
0
18.2 Hz, C1 H3), 3.41 (d, 3H, 3JH–P = 11.3 Hz,
0
C2H3), 3.66, 3.67 (2 · s, 6H, C5H3, C5 H3), 3.76 (d, 3H,
0
3JH–P = 11.3 Hz, C2 H3), 5.78 (d, 1H, JH–P = 8.9 Hz,
3
0
C3H), 5.82 (d, 1H, JH–P = 8.7 Hz, C3 H), 7.31–7.43
(2 · m, 10H, Ph); 13C NMR (125 MHz, CDCl3): d =
3
4.7. (S)-Methyl 2-(diphenylphosphinooxy)propanoate 8
1
1
11.31 (d, JC–P = 146.4 Hz, C1H3), 11.41 (d, JC–P = 145.9
0
Hz, C1 H3), 51.260 (d, JC–P = 7.1 Hz, C2H3), 52.00 (d,
3
Methyl-(S)-lactate (2 g, 19.2 mmol, 1.8 mL) was dissolved
in dry ether (50 mL) and to the resulting solution triethyl-
amine (2.9 g, 28.9 mmol, 4 mL) was added at 0 ꢂC under
argon atmosphere. Then chlorodiphenylphosphine (4.3 g,
19.2 mmol, 3.6 mL) was added dropwise at this tempera-
ture. Next, the temperature was raised to 20 ꢂC and after
30 min a white precipitate was filtered off. The filtrate
was evaporated and the crude 8 was used in the next oxida-
tion reaction to 9.
0
3JC–P = 6.8 Hz, C2 H3), 52.45, 52.50 (2 · s, C5H3, C5 H3),
2
2
75.06 (d, JC–P = 4.9 Hz, C3H), 75.33 (d, JC–P = 5.5 Hz,
0
C3 H), 127.02, 127.11, 128.60, 128.63, 129.03, 129.09 (C–
Ph), 169.490 (d, JC–P = 4.7 Hz, C4), 169.65 (d, JC–P
=
3
3
4.4 Hz, C4 ); IR (film): m/cmꢀ1 3010, 2955, 1757,
1455,1437, 1219, 1065, 992, 917, 757, 731; MS-CI (isobu-
tane): m/z (%) 259 (M++1, 100); MS-HR-CI: M++1,
found: 259.0735 for C11H16O5P—calculated 259.0735.
Crude 8. Purity: ca. 90% based on 31P NMR; yellow oil; 31
P
4.6.3. (RC,RP+SP)-Methyl 2-(methoxy(methyl)phosphoryl-
oxy)-2-phenylacetate 6c.
NMR (81 MHz, CDCl3): d = 116.12 ppm; 1H NMR
3
(200 MHz, CDCl3): d = 1.54 (d, 3H, JH–H = 6.9 Hz,
2, 2'
OMe O
3, 3'
3
O
P
1, 1'
CH–CH33), 3.68 (s, 3H, COOCH3), 4.54 (dq, 1H, JH–P
=
Me
5, 5'
9.5 Hz, JH–H = 6.9 Hz, CH–CH3), 7.2–7.7 (m, 10H,
O
(C6H5)2P); 13C NMR (50 MHz, CDCl3): d = 19.94 (s,
4, 4'OMe
2
Ph
H
CH–CH3), 51.94 (s, COOCH3), 74.74 (d, JC–P = 21.6 Hz,
CH–CH3), 128–142 (many signals, (C6H5)2P), 172.95 (s,
C@O); MS-EI (70 eV): m/z (%) = 288 (M+, 0.6), 273
(M+ꢀMe, 23), 201 (Ph2P@O+, 100); MS-HR-EI: M+,
found: 288.0918 for C16H17O3P—calculated 288.0915.
25
Yield: 63%; a colourless liquid; ½aꢂ589 ¼ ꢀ98:85 (c 2.0,
CHCl3); 31P NMR (81 MHz, CDCl3): d = 33.85,
1
33.73 ppm, (1:0.8); H NMR (500 MHz CDCl3) d = 1.34
(d, 3H, JH–P = 18.3 Hz, C1H3), 1.63 (d, 3H, JH–P
=
2
2
0
18.3 Hz, C1 H3), 3.43 (d, 3H, JH–P = 11.5 Hz, C2H3),
4.8. (S)-Methyl 2-(diphenylphosphoryloxy)propanoate 9
3
0
3.69, 3.70 (2 · s, 6H, C5H3, C5 H3), 3.78 (d, 3H, JH–P
=
3
0
11.6 Hz, C2 H3), 5.80 (d, 1H, JH–P = 9.0 Hz, C3H), 5.84
The compound 8 (1.08 g, 3.75 mmol) was dissolved in
methanol (10 mL) and to the resulting solution hydrogen
peroxide (30%, 11.25 mmol, 1.15 mL) was added dropwise
at ꢀ20 ꢂC. After 1 h, the reaction mixture was partitioned
between CH2Cl2 and H2O. The organic layer was washed
with water, dried over MgSO4, filtered and evaporated to
afford 1.19 g of the crude product 9.
3
0
(d, 1H, JH–P = 8.7 Hz, C3 H), 7.31–7.43 (2 · m, 10H,
3
Ph); 13C NMR (125 MHz, CDCl3): d = 11.40 (d, JC–P
=
1
0
146.5 Hz, C1H3), 11.51 (d, JC–P = 145.7 Hz, C1 H3),
1
51.35 (d, JC–P = 6.9 Hz, C2H3), 52.10 (d, JC–P = 7.0 Hz,
3
3
0
0
C2 H3), 52.59, 52.59 (2 · s, C5H3, C5 H3), 75.16 (d,
0
2JC–P = 4.9 Hz, C3H), 75.43 (d, JC–P = 5.3 Hz, C3 H),
2