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V. V. Nesterov, O. I. Kolodiazhnyi / Tetrahedron 63 (2007) 6720–6731
4.4. General procedure for the reduction of keto-
phosphonates 1a–f with NaBH4/(R,R)-TA adduct
6.42%]; [a]2D0 ꢀ83.7 (c 1.3, CHCl3); dH (300 MHz, C6D6)
7.45 (2H, m, C6H4), 6.9 (3H, t, J 8.2, C6H4), 5.18 (1H, br,
OH), 4.2 (2H, m, OCH), 4.04 (1H, d, J 22.5 Hz, CHP),
2.25–1.00 (14H, m, CH3 and CH), 2.0 (1H, m, CH(CH3)2),
1.74 (1H, m, CH(CH3)2), 0.91 (3H, d, J 6.9 Hz, CH3), 0.86
(6H, d, J 6.9 Hz, CH3), 0.76 (6H, d, J 6.9 Hz, CH3), 0.71
(3H, d, J 6.9 Hz, CH3); dC (100.6 MHz, CDCl3) 164.2,
164.1, 161.6, 161.5, 130.7, 130.4, 130.3, 130.2, 125.8,
116.4, 116.1, 114.2, 114.4, 72.4, 70.8, 49.3, 49.16, 49.0,
48.3, 45.7, 42.5, 34.0, 31.5, 25.3, 22.7, 22.0, 21.1, 21.0,
15.7, 15.6; dP (121.4 MHz, CDCl3) 19.8.
To a suspension of sodium borohydride (0.36 g, 10 mmol) in
50 mL of THF was added (R,R)-(+)-tartaric acid (1.5 g,
10 mmol), then the reaction mixture was refluxed for 4 h.
After that a solution of ketophosphonate (2.5 mmol) in
10 mL of THF was added at ꢀ30 ꢂC and the reaction mixture
was stirred at this temperature for 24 h. Then to the reaction
mixture was added 20 mL of ethyl acetate and 30 mL of 1 N
hydrochloric acid dropwise. The organiclayer was separated,
the aqueous phase was saturated with NaCl and extracted
two times with ethyl acetate (15 mL). The organic extracts
werewashed with a saturated solution of Na2CO3 (3ꢄ20 mL)
and dried with Na2SO4. The solvent was removed under
vacuum, the residue was crystallized from acetonitrile.
4.4.6. Di(1R,2S,5R)-menthyl (S)-hydroxy(2-methoxyphe-
nyl)methylphosphonate 2f (Table 1, entry 6). Yield: 74%,
white solid, mp 116–117 ꢂC (MeCN); [found: C, 68.16; H,
9.50; P, 6.25. C28H47O5P requires C, 67.99; H, 9.58; P,
6.26%]; [a]2D0 ꢀ75.2 (c 0.66, CHCl3); dH (300 MHz, C6D6)
7.60 (1H, d, J 7.5 Hz, C6H4), 7.04 (1H, t, J 7.9 Hz, C6H4),
6.80 (1H, t, J 7.9 Hz, C6H4), 6.59 (1H, d, J 8.1 Hz, C6H4),
5.24 (1H, d, J 13.2 Hz, CHP), 4.54 (1H, br, OH), 4.17 (1H,
m, OCH), 4.03 (1H, m, OCH), 3.59 (3H, s, OCH3), 2.40
(1H, m, CH(CH3)2), 2.14 (1H, m, CH(CH3)2), 1.54–0.92
(14H, m, CH2 and CH), 0.84 (3H, d, J 6.9 Hz, CH3), 0.79
(6H, m, 2CH3), 0.73 (3H, d, J 6.9 Hz, CH3), 0.52 (3H, d, J
6.9 Hz, CH3), 0.60 (3H, d, J 6.9 Hz, CH3); dC (100.6 MHz,
CDCl3) 157.10 (d, J 6.5 Hz), 129.00 (d, J 2.8 Hz), 128.8
(d, J 2.8 Hz), 128.8 (d, J 2.0 Hz), 125.3 (d, J 5.5 Hz),
120.6 (d, J 2.0 Hz), 110.5, 66.6 (d, J 161 Hz), 55 (s), 48.8
(d, J 35 Hz), 48.5 (d, J 34 Hz), 43.8, 34.09, 33.9, 31.5,
25.24, 22.7, 21.97, 21.87, 21.21, 21.05, 15.72, 15.62; dP
(121.4 MHz, CDCl3) 20.98.
4.4.1. Diethyl (S)-hydroxy(phenyl)methylphosphonate 2a
(Table 1, entry 1). Yield: 95%, white solid, mp 74–76 ꢂC;
[found: C, 54.08; H, 6.98; P, 12.66. C11H17O4P requires C,
54.10; H, 7.02; P, 12.68%]; [a]2D0 ꢀ15.4 (c 2.6, CHCl3); dH
(300 MHz, C6D6) 7.49 (2H, m, Ph), 7.3–7.38 (3H, m, Ph),
5.01 (1H, d, J 10.9 Hz, CHOH), 3.90–4.13 (4H, m, 2CH2),
3.8 (1H, br, OH), 1.26 (3H, t, J 7.1 Hz, CH3), 1.21 (3H, t,
J 7.1 Hz, CH3); dP (121.4 MHz, CDCl3) 22.00.5
4.4.2. Diethyl (R)-hydroxy(phenyl)methylphosphonate
2b (Table 1, entry 2). Yield: 94%, white solid, mp 74–
76 ꢂC; [a]D20 +28.3 (c 2.1, CHCl3), that corresponds to.32a
4.4.3. Di(1R,2S,5R)-menthyl (S)-hydroxy(phenyl)methyl-
phosphonate 2d (Table 1, entry 3). Yield: 80%, white solid,
mp 112–113 ꢂC (MeCN); [found: C, 69.53; H, 9.80; P, 6.38.
C27H45O4P requires C, 69.80; H, 9.76; P, 6.67%]; [a]D20
ꢀ87.6 (c 1.3, CHCl3); dH (300 MHz, C6D6) 7.8 (2H, m, Ph),
7.48 (3H, m, Ph), 5.2 (1H, d, J 10.5 Hz, CHP), 5.10 (1H, br,
OH), 4.49 (2H, m, 2OCH), 2.6–1.40 (14H, m, CH3 and CH),
2.4 (1H, m, CH(CH3)2), 2.00 (1H, m, CH(CH3)2), 1.21 (3H,
d, J 6.9 Hz, CH3), 1.20 (3H, d, J 6.9 Hz, CH3), 1.18 (3H, d, J
6.9 Hz, CH3), 1.08 (3H, d, J 6.9 Hz, CH3), 1.01 (3H, d, J
6.9 Hz, CH3), 1.04 (3H, d, J 6.9 Hz, CH3); dC (100.6 MHz,
CDCl3) 127.98 (d, J 2.5 Hz), 127.8 (d, J 2.5 Hz), 127.4 (d,
J 9.6 Hz), 71.8 (d, J 160 Hz), 48.4 (d, J 14 Hz), 48.3 (d, J
13.2 Hz,), 45.66, 42.53, 34.01, 31.5, 25.33, 22.7, 21.98,
21.13, 21.03, 15.73, 15.61; dP (121.4 MHz, CDCl3) 22.3.
4.4.7. Di(1R,2S,5R)-menthyl (S)-hydroxy(piperonyl)me-
thylphosphonate 2g (Table 1, entry 7). Yield: 70%, white
solid, mp 96 ꢂC (MeCN); [found: C, 66.17; H, 8.83; P, 6.14.
C28H45O6P requires C, 66.12; H, 8.92; P, 6.09%]; [a]2D0 ꢀ74
(c 1, CHCl3); dH (300 MHz, C6D6) 6.98 (1H, s, C6H3), 6.85
(1H, d, J 7.9 Hz, C6H3), 6.57 (1H, d, J 7.9 Hz, C6H3), 5.65
(2H, s, O2CH2), 5.38 (1H, br, OH), 4.7 (1H, d, J 10.5 Hz,
CHP), 4.09 (2H, m, OCH), 1.94 (1H, m, CH(CH3)2), 1.48
(1H, m, CH(CH3)2), 2.27–0.9 (16H, m, CH2 and CH), 0.81
(3H, d, J 6.9 Hz, CH3), 0.77 (3H, d, J 6.9 Hz, CH3),
0.76 (3H, d, J 6.9 Hz, CH3), 0.67 (3H, d, J 6.9 Hz, CH3),
0.66 (3H, d, J 6.9 Hz, CH3), 0.62 (3H, d, J 6.9 Hz, CH3);
dP (121.4 MHz, CDCl3) 19.8.
4.4.4. Di(1R,2S,5R)-menthyl (R)-hydroxy(phenyl)me-
thylphosphonate 2c (Table 1, entry 4). Yield: 95%, white
solid, mp 139 ꢂC (hexane); [found: C, 69.75; H, 9.60; P, 6.56.
C27H45O4P requires C, 69.80; H, 9.76; P, 6.67%]; [a]2D0 ꢀ70
(c 1.07, CHCl3); dH (300 MHz, C6D6) 7.5–7.3 (2H, m, Ph),
7.3–7.2 (3H, m, Ph), 4.92 (1H, d, J 11 Hz, CHP), 4.2 (2H,
dt, J 4.1, 2.3 Hz, 2OCH), 3.7 (1H, br, OH), 1.23–1.1 (18H,
m, CH2+CH), 1.0–0.7 (18H, m, CH3); dC (100.6 MHz,
CDCl3) 127.99 (d, J 2.5 Hz), 127.8 (d, J 2.5 Hz), 127.3 (d,
JCP 9.6 Hz), 71.6 (d, J 160 Hz), 48.6 (d, J 14 Hz), 48.5 (d, J
13.2 Hz), 45.66, 42.53, 34.00, 31.5, 25.31, 22.7, 21.97,
21.13, 21.03, 15.74, 15.60; dP (CDCl3) 23.71.
4.4.8. Di(1R,2S,5R)-menthyl (S)-hydroxy(isopropyl)me-
thylphosphonate 2h (Table 1, entry 8). Yield: 97.6%, white
solid, mp 71 ꢂC (MeCN); [found: C, 66.90; H, 10.93; P, 7.18.
C24H47O4P requires C, 66.94; H, 11.0; P, 7.19%]; [a]D20
ꢀ82.8 (c 2.2, CHCl3); dH (300 MHz, C6D6) 4.09 (2H, m,
2OCH), 3.33 (1H, m, CHOH), 2.3–0.87 (18H, m, CH2 and
CH), 1.94 (1H, m, CH(CH3)2), 0.97 (3H, d, J 6.3 Hz,
CH(CH3)2), 0.95 (3H, d, J 6.3 Hz, CH(CH3)2), 0.73–0.84
(18H, m, CH3); dP (121.4 MHz, CDCl3) 24.04.
4.4.9. Diethyl (R)-2-hydroxy-2-phenylethylphosphonate
8a (Table 1, entry 9). Yield: 95%, yellow oil; [found: C,
55.86; H, 7.47; P, 11.90. C12H19O4P requires C, 55.81; H,
7.42; P, 11.99%]; [a]D20 ꢀ25 (c 2.38, CHCl3); dH (300 MHz,
C6D6) 7.28 (2H, d, J 7.2 Hz, C6H5), 7.14 (2H, t, J 7.2 Hz,
C6H5), 7.05 (1H, t, J 7.2 Hz, C6H5), 5.06–4.96 (1H, m,
CHOH), 4.75 (1H, br, OH), 3.99–3.77 (4H, m, 2CH2),
4.4.5. Di(1R,2S,5R)-menthyl (S)-hydroxy(2-fluorophe-
nyl)methylphosphonate 2e (Table 1, entry 5). Yield: 97%,
white solid, mp 137.5–138.5 ꢂC (MeCN); [found: C, 67.00;
H, 9.20; P, 6.38. C27H44FO4P requires C, 67.20; H, 9.19; P,