B. Breit, P. Demel / Tetrahedron 56 (2000) 2833±2846
2841
Flash chromatography with petroleum ether/tert-butyl
methyl ether furnished the 1,4-addition products 4a±g as
colorless, highly viscous oils.
Ethyl (3Rp,5Rp,6Sp,7Sp)-(^)-8-[2,2-(dimethyl)propionyl-
oxy]-6-[2-(diphenylphosphanyl)-benzoyloxy]-3,5,7-
trimethyloctanoate (4f). From 280 mg (0.465 mmol) 3d
was obtained 172 mg (60%) of 4f. Diastereomer ratio rela-
tive to newly formed stereogenic center (anti:syn, 85:15).
1H NMR (300 MHz, CDCl3): d0.84 (m, 9H, 3 CH3), 1.08
(m, 1H) 1.17 [s, 9H, C(CH3)3], 1.2 (t, J7.1 Hz, 3H, CH3),
1.22 (m, 1H), 1.78±2.2 (m, 5H), 3.85 (m, 2 H OCH2), 4.08
(m, 2H, OCH2), 5.0 (pseudo t, J5.8 Hz, 1H, OCH), 6.91
(m, 1H, ArH), 7.2±7.4 (m, 12H, ArH), 8.1 (m, 1H, ArH).
13C NMR (75.469 MHz, CDC13): d12.31, 13.93, 14.18,
18.83, 27.1 (3 C) 27.50, 32.07, 34.27, 38.71, 40.27, 42.64,
60.03, 66.19, 78.65, 128.09, 128.34 (d, JC,P7.3 Hz, 4 C)
128.48 (d, JC,P2.3 Hz, 2 C), 130.49 (d, JC,P2.3 Hz),
Ethyl (3Rp,5Rp,6Rp)-(^)-6-[2-(diphenylphosphanyl)ben-
zoyloxy]-3,5,7-trimethyloctanoate (4a). From 2.535 g
(5.044 mmol) 3a was obtained 2.43 g (93%) of 4a. Dia-
stereomer ratio relative to newly formed stereogenic center
1
(anti:syn, 95:5). H NMR (300 MHz, CDCl3): d0.7 (m,
12H, 4 CH3), 1.0 (m, 1H), 1.1 (m, 4H), 1.7±2.1 (m, 5H),
4.0 (q, J7.2 Hz, 2H, OCH2), 4.7 (dd, J7.2, 5.0 Hz, 1H,
HCO), 6.8 (m, 1H, ArH), 7.2±7.3 (m, 12H, ArH), 8.0 (m,
1H, ArH). 13C NMR (75.469 MHz, CDCl3): d13.51,
14.23, 17.98, 19.05, 19.30, 27.62, 29.45, 31.80, 40.54,
42.62, 59.99, 82.80, 128.05, 128.35 (d, JC,P7.2 Hz, 4 C),
129.45 (2 C), 130.45, 131.76, 133.90 (d, JC,P20.8 Hz, 2 C),
134.0 (d, JC,P21.1 Hz, 2 C), 134.21 (C10 expected at ca.
134 as a doublet is obscured by the signals at 134.0±
134.21), 138.21 (d, JC,P12.2 Hz, 2 C), 141.15 (d,
JC,P28.3 Hz), 166.30 (d, JC,P2.6 Hz), 172.7 8. 31P NMR
(81.015 MHz, CDCl3): d22.8 C32H39O4 P(518.6): calcd C
74.11, H 7.58; found C 74.08, H 7.63.
131.88, 133.84 (d, JC,P20.7 Hz,
2 C), 133.94 (d
JC,P17.9 Hz), 133.96 (d, JC,P21.0 Hz, 2 C), 134.28,
138.0 (d, JC,P12.1 Hz, 2 C), 140.0 (d, JC,P28.0 Hz),
166.03 (d, JC,P2.8 Hz), 172.74, 178.25. 31P NMR
(81.015 MHz, CDCI3): d23.3. C37H47O6F (618.7): calcd
C 71.82, H 7.66; found C 71.60, H 7.35.
Ethyl (3R,5R,6S,7S)-(2)-6-[2-(diphenylphosphanyl)ben-
zoyloxyl-8-[(4R)-isopropyl-2-oxazolidin-3-yl]-3,5,7-
trimethyloctanoate [(2)-4g]. From 280 mg (0.435 mmol)
(2)-3e was obtained 242 mg (85%) of (2)-4g. Diastereo-
mer ratio relative to newly formed stereogenic center
Diethyl (3Rp,5Rp,6Sp,7Sp)-(^)-6-[2-(diphenylphosphanyl)-
benzoyloxy]-3,5,7-trimethyloctandioate
(4d).
From
670 mg (1.195 mmol) 3b was obtained 472 mg (68%) of
4d. Diastereomer ratio relative to newly formed stereogenic
center (anti:syn, 95:5). 1H NMR (300 MHz, CDCl3):
d0.74 (d, J6.7 Hz, 3H, CH3), 0.80 (d J7.2 Hz, 3H,
CH3), 1.05 (d, J7.2 Hz, 3H, CH3), 1.06 (t, J7.1 Hz,
3H, CH3), 1.15 (t, J7.3 Hz, 3H, CH3), 1.0±1.2 (m, 2H),
1.8±2.1 (m, 4H), 2.75 (pseudo quintett, J7.2 Hz, 1H), 3.93
(q, J7.1 Hz, 2H, OCH2), 4.03 (q, J7.1 Hz, 2H, OCH2),
5.10 (dd, J7.4, 4.7 Hz, 1H, OCH), 6.84 (m, 1H, ArH)
7.12±7.35 (m, 12H, ArH), 8.04 (m, 1H, ArH). 13C NMR
(75.469 MHz, CDCl3): d13.23, 13.86, 13.98, 14.16,
18.87, 27.49, 31.68, 40.06, 41.98, 42.47, 59.97, 60.47,
78.59, 128.10, 128.29 (d, JC,P7.7 Hz, 4 C), 128.38 (2 C),
130.60 (d, JC,P2.2 Hz), 131.85, 133.70 (d, JC,P20.6 Hz, 2
C), 133.82 (d, JC,P18.5 Hz), 133.91 (d, JC,P20.8 Hz, 2 C),
134.19, 138.0 (d, JC,P17.1 Hz), 138.17 (d, JC,P16.7 Hz)
141.0 (d, JC,P28.1 Hz), 165.48 (d, JC,P2.4 Hz), 172.73,
173.47. 31P NMR (81.015 MHz, CDCl3): d23.8.
C34H41O6P (576.7): calcd C 70.82, H 7.17; found C 70.92,
H 7.00.
1
(anti:syn, 95:5). [a]D235.7 (c1.85, CH2Cl2). H NMR
(300 MHz, CDCl3): d0.42 (d, J6.9 Hz, 3H, CH3), 0.68
(d, J7.1 Hz, 3H, CH3), 0.72 (d, J6.3 Hz, 3H, CH3), 0.82
(d, J6.8 Hz, 3H, CH3), 1.06 (d, J7.0 Hz, 3H, CH3), 1.18
(t, J7.2 Hz, 3H, CH3), 1.8±2.1 (m, 7H), 4.1 (m, 4H), 4.30
(m, 2H), 5.36 (dd, J9.5, 2.8 Hz, 1H, OCH), 6.82 (m, 1H,
ArH), 7.1±7.4, m, 12H, ArH 8.0 (m, 1H, ArH). 13C NMR
(75.469 MHz, CDCl3): d12.91, 14.31 (2 C), 14.82, 18.11,
19.11, 27.61, 28.19, 31.54, 39.73, 40.53, 42.47, 58.66,
60.09, 63.01, 78.57, 128.17, 128.33 (d, JC,P7.1 Hz, 2 C),
128.43 (d, JC,P8.1 Hz, 2 C), 128.58 (2 C), 130.78, 131.97,
133.57 (d, JC,P20.2 Hz, 2 C), 133.94 (d, JC,P18.8 Hz),
134.27 (d, JC,P21.3 Hz, 2 C), 134.41, 138.36 (d,
JC,P13.8 Hz), 138.37 (d, JC,P11.0 Hz), 141.21 (d,
JC,P28.6 Hz), 153.8, 165.2 (d, JC,P2.5 Hz), 173.0,
174.20. 31P NMR (81.015 MHz, CDCl3): d23.1
C38H46NO7P (659.8): calcd C 69.07, H 7.17, N 2.12;
found C 68.86, H 7.09, N 2.30.
Ethyl (3Rp,5Rp,6Rp)-(^)-3-Butyl-5,7-dimethyl-6-[2-(di-
phenylphosphanyl)benzoyloxy]-octanoate (4b). A similar
procedure as described for the addition of dimethylcuprate
was employed, except di-n-butylcuprate was prepared at
2308C. From 251 mg (0.5 mmol) 3a was obtained 190 mg
(68%) of 4b, as a colorless, highly viscous oil. Diastereomer
ratio relative to newly formed stereogenic center (anti:syn,
Ethyl (3Rp,5Rp,6Sp,7Rp)-(^)-6-[2-(diphenylphosphanyl)-
benzoyloxy]-3,5,7-trimethyl-8-(triphenyl)methoxy-
octanoate (4e). From 1.251 g (1.644 mmol) 3c was
obtained 910 mg (71%) of 4e. Diastereomer ratio relative
1
to newly formed stereogenic center (anti:syn, 86:14). H
NMR (300 MHz, CDCl3): d0.76 (d, J6.2 Hz, 3H,
CH3), 0.77 (d J6.6 Hz, 3H, CH3), 1.07, (d, J6.7 Hz,
3H, CH3), 1.12 (t, J7.1 Hz, 3H, CH3), 1.2±1.4 (m, 2H)
1.7±2.04 (m, 5H), 3.0 (m, 1H), 3.2 (m, 1H), 4.1 (q,
J7.1 Hz, 2H, OCH2), 4.92 (dd, J6.8, 5.2 Hz, 1H,
OCH), 6.9 (m, 1H, ArH), 7.1±7.5 (m, 27H, ArH), 7.84
(m, 1H, ArH). 13C NMR (75.469 MHz, CDC13): d13.71,
14.33, 15.21, 18.97, 27.62, 31.79, 35.91, 40.33, 42.69,
60.06, 64.77, 80.04, 86.62, 126.83±144.3 (all Aryl-C),
166.0, 172.90. 31P NMR (81.015 MHz, CDCl3): d23.3.
C51H53O5P (777.0): calcd C 78.84, H 6.88; found C 78.75, H
6.58.
1
95:5). H NMR (300 MHz, CDCl3): d0.8 (d, J6.6 Hz,
3H, CH3), 0.84±1.5 (m, 19H), 1.6 (m, 1H), 1.8±2.0 (m, 3H),
2.1 (m, 1H), 2.3 (dd, J14.7, 6.0 Hz, 1H, CH2), 4.09 (m, 2H,
OCH2), 4.8 (dd, J7.2, 4.7 Hz, 1H, OCH), 6.92 (m, 1H,
ArH), 7.2±7.4 (m, 12H, ArH), 8.1 (m, 1H, ArH). 13C
NMR (75.469 MHz, CDCl3): d14.03, 14.16, 14.38,
18.22, 19.48, 23.09, 28.34, 29.67, 31.96, 32.44, 33.04,
38.47, 39.82, 60.17, 82.84, 128.2, 128.51 (d, JC,P7.1 Hz,
4
C), 128.56 (2 C), 130.59, 131.89, 133.97 (d,
JC,P20.4 Hz), 134.11 (d, JC,P20.8 Hz, 4 C), 134.42,
138.43 (d, JC,P12.8 Hz, 2 C), 144.25 (d, JC,P28.1 Hz),