Notes
J . Org. Chem., Vol. 61, No. 24, 1996 8669
NMR (300 MHz, CDCl3) δ 0.00 (s, 9H, Me3Si), 2.12 (s, 1H, OH),
2.24 (dd, 1H, J ) 14.0, 10.0 Hz, 2-H), 2.49 (ddd, 1H, J ) 14.0,
3.4, 1.0 Hz, 2-H), 4.63 (m, 1H, 1-H), 5.43 (d, 1H, J ) 2.7 Hz,
4-H), 5.59 (m, 1H, 4-H), 7.33 (d, 2H, J ) 8.2 Hz, Ph), 7.45 (d,
2H, J ) 8.2 Hz, Ph); 13C NMR (75 MHz, CDCl3) δ -1.4, 47.0,
71.6, 125.3, 125.4, 126.1, 128.8, 148.1, 148.8; MS (CI, NH3) m/ z
306, 288, 271; HRMS (CI, NH3) calcd for C14H23F3NOSi [M +
NH4]+ 306.1501, found [M + NH4]+ 306.1497. Anal. Calcd for
1-[4-(Tr iflu or om eth yl)p h en yl]-3-(p h en yld im eth ylsilyl)-
3-bu ten -1-ol (5i): Rf 0.26 (4:1 hexanes:Et2O); IR (film) 3433,
3052, 2957, 2907, 1620, 1424, 1326, 1253, 1164, 1125, 1067, 1016
cm-1; 1H NMR (300 MHz, CDCl3) δ 0.36 (s, 3H, CH3Si), 0.37 (s,
3H, CH3Si), 2.00 (d, 1H, J ) 2.2 Hz, OH), 2.28 (dd, 1H, J )
14.0, 9.9 Hz, 2-H), 2.49 (dd, 1H, J ) 14.0, 2.5 Hz, 2-H), 4.44 (m,
1H, 1-H), 5.59 (d, 1H, J ) 2.7 Hz, 4-H), 5.76 (m, 1H, 4-H), 7.19
(d, 2H, J ) 8.0 Hz, Ph), 7.25-7.35 (m, 3H, Ph), 7.40-7.50 (m,
4H, Ph); 13C NMR (75 MHz, CDCl3) δ -3.0, -2.9, 47.2, 71.6,
125.0, 125.2, 125.3, 126.0, 128.1, 129.5, 130.4, 133.9, 137.4, 147.2,
148.0; MS (CI, NH3) m/ z 368, 350, 333, 290, 272; HRMS (CI,
NH3) calcd for C19H25F3NOSi [M + NH4]+ 368.165, found [M +
NH4]+ 368.1655. Anal. Calcd for C19H21F3OSi: C, 65.12; H,
6.04. Found: C, 65.16; H, 5.89.
C
14H19F3OSi: C, 58.31; H, 6.65. Found: C, 58.60; H, 6.77.
1-[2-(Tr iflu or om eth yl)ph en yl]-3-(tr im eth ylsilyl)-3-bu ten -
1-ol (5d ): Rf 0.26 (4:1 hexanes:Et2O); IR (film) 3465, 3052, 2957,
1
2904, 1609, 1454, 1409, 1313, 1251, 1162, 1121, 1036 cm-1; H
NMR (300 MHz, CDCl3) δ 0.00 (s, 9H, Me3Si), 2.03 (br s, 1H,
OH), 2.18 (dd, 1H, J ) 14.0, 10.7 Hz, 2-H), 2.54 (d, 1H, J ) 14.0
Hz, 2-H), 5.01 (d, 1H, J ) 10.7 Hz, 1-H), 5.46 (d, 1H, J ) 2.9
Hz, 4-H), 5.66 (m, 1H, 4-H), 7.21 (t, 1H, J ) 7.5 Hz, Ph), 7.43 (t,
1H, J ) 7.5 Hz, Ph), 7.46 (d, 1H, J ) 7.5 Hz, Ph), 7.67 (d, 1H,
J ) 7.5 Hz, Ph); 13C NMR (75 MHz, CDCl3) δ -1.5, 47.1, 67.3,
122.7, 125.3, 125.4, 127.4, 127.8, 129.1, 132.3, 143.4, 149.3; MS
(CI, NH3) m/ z 306, 288, 271, 247; HRMS (CI, NH3) calcd for
2-(P h en yld im eth ylsilyl)-1-n on en -4-ol (5j): Rf 0.26 (4:1
hexanes:Et2O); IR (film) 3391, 3068, 3050, 2955, 2929, 2871,
1
2859, 1458, 1428, 1411, 1378, 1250, 1111, 1069, 1038 cm-1; H
NMR (300 MHz, CDCl3) δ 0.19 (s, 3H, CH3Si), 0.20 (s, 3H, CH3-
Si), 0.66 (t, 3H, J ) 7.0 Hz, 9-H), 0.90-1.25 (m, 8H, 4 × CH2),
1.35 (d, 1H, J ) 2.7 Hz, OH), 1.93 (dd, 1H, J ) 13.7, 9.4 Hz,
3-H), 2.19 (ddd, 1H, J ) 13.7, 3.5, 0.9 Hz, 3-H), 3.27 (m, 1H,
4-H), 5.38 (d, 1H, J ) 2.9 Hz, 1-H), 5.59 (m, 1H, 1-H), 7.10-
7.20 (m, 3H, Ph), 7.25-7.35 (m, 2H, Ph); 13C NMR (75 MHz,
CDCl3) δ -2.9, -2.8, 14.1, 22.6, 25.3, 31.8, 37.0, 45.0, 69.6, 127.9,
129.2, 129.5, 133.8, 137.8, 147.8; MS (CI, NH3) m/ z 294, 276,
259, 199; HRMS (CI, NH3) calcd for C17H32NOSi [M + NH4]+
C
14H23F3NOSi [M + NH4]+ 306.1501, found [M + NH4]+ 306.1491.
1-(4-Nitr op h en yl)-3-(tr im eth ylsilyl)-3-bu ten -1-ol (5e): Rf
0.26 (4:1 hexanes:EtOAc); IR (film) 3551, 3442, 3051, 2954, 2902,
1
1603, 1521, 1408, 1347, 1249, 1190, 1109, 1060, 1013 cm-1; H
NMR (300 MHz, CDCl3) δ 0.00 (s, 9H, Me3Si), 2.15 (d, 1H, J )
1.9 Hz, OH), 2.20 (dd, 1H, J ) 13.9, 10.1 Hz, 2-H), 2.50 (dd, 1H,
J ) 13.9, 2.3 Hz, 2-H), 4.67 (m, 1H, 1-H), 5.45 (d, 1H, J ) 2.6
Hz, 4-H), 5.59 (m, 1H, 4-H), 7.38 (d, 2H, J ) 8.7 Hz, Ph), 8.04
(d, 2H, J ) 8.7 Hz, Ph); 13C NMR (75 MHz, CDCl3) δ -1.3, 47.0,
71.4, 123.7, 126.5, 129.2, 147.3, 148.5, 151.5; MS (CI, NH3) m/ z
283, 265, 250, 234, 218; HRMS (CI, NH3) calcd for C13H23N2O3-
Si [M + NH4]+ 283.1478, found [M + NH4]+ 283.1477. Anal.
Calcd for C13H19NO3Si: C, 58.84; H, 7.22; N, 5.28. Found: C,
59.07; H, 6.94; N, 5.28.
294.2253, found [M + NH4]+ 294.2246. Anal. Calcd for C17H28
OSi: C, 73.86; H, 10.22. Found: C, 73.59; H, 9.97.
-
Gen er a l P r oced u r e for th e Syn th esis of Mosh er Ester s.
DMAP (cat.), pyridine (40 µL, 0.5 mmol), and (R)-(-)-R-methoxy-
R-(trifluoromethyl)phenylacetyl chloride (11 µL, 0.06 mmol) were
added to alcohol 5 (0.05 mmol) in CH2Cl2 (0.1 mL) under N2.
The mixture was stirred at room temperature until the reaction
was complete (TLC, ca. 4 h), diluted with Et2O (5 mL), and
washed sequentially with saturated aqueous CuSO4 (2 × 2 mL),
saturated aqueous NaHCO3 (2 × 2 mL), 1 M HCl (2 mL), and
brine (2 mL). The organic phase was dried (MgSO4), evaporated,
dissolved in Et2O, and filtered through silica gel, which was
further washed with Et2O, and reevaporated under reduced
pressure to give the Mosher ester(s), which was analyzed directly
by 1H NMR.
(4R)-2,2-Dim eth yl-4-[(1S/R)-1-h yd r oxy-3-(tr im eth ylsilyl)-
3-bu ten -1-yl]-1,3-d ioxola n e (5f). Mixture of isomers (1S:1R
85:15): Rf 0.26 (4:1 hexanes:EtOAc); IR (film) 3482, 3048, 2986,
1
2954, 2897, 1439, 1408, 1375, 1250, 1216, 1156, 1065 cm-1; H
NMR (300 MHz, CDCl3) δ 0.00 (s, 9H, Me3Si), 1.25 (s, 3H, Me),
1.32 (s, 3H, CH3), 1.88 (d, 0.85H, J ) 1.9 Hz, OH), 2.03 (dd, 1H,
J ) 13.9, 9.9 Hz, 2-H), 2.18 (d, 0.15H, J ) 6.6 Hz, OH), 2.42
(dd, 1H, J ) 13.9, 3.4 Hz, 2-H), 3.52 (m, 0.15H, 1-H), 3.63 (m,
0.85H, 1-H), 3.80-4.00 (m, 3H, dioxolane-H), 5.38 (d, 1H, J )
2.8 Hz, 4-H), 5.57 (m, 0.85H, 4-H), 5.60 (m, 0.15H, 4-H); 13C NMR
(75 MHz, CDCl3) δ -1.3, 25.3, 26.6, 40.4, 40.5, 65.5, 66.1, 69.8,
70.6, 78.5, 109.1, 127.9, 148.2, 148.6; MS (CI, NH3) m/ z 262,
227, 209, 204, 187; HRMS (CI, NH3) calcd for C12H25O3Si [M +
H]+ 245.1573, found [M + H]+ 245.1562. Anal. Calcd for
(4R/S)-4-[(S)-r-Met h oxy-r-(t r iflu or om et h yl)p h en yla ce-
toxy]-4-(4-p yr id yl)-2-(tr im eth ylsilyl)-1-bu ten e. 1:1 Mixture
of diastereoisomers: Rf 0.45 (1:1 hexanes:EtOAc); 1H NMR (300
MHz, CDCl3) δ -0.02 (s, 9H, Me3Si), 0.00 (s, 9H, Me3Si), 2.35-
2.50 (m, 2H, 3-H), 2.55-2.70 (m, 2H, 3-H), 3.33 (s, 3H, CH3O),
3.41 (s, 3H, CH3O), 5.24 (d, 1H, J ) 2.2 Hz, 1-H), 5.34 (m, 1H,
1-H), 5.38 (d, 1H, J ) 2.2 Hz, 1-H), 5.51 (m, 1H, 1-H), 5.85-
6.00 (m, 2H, 2 × 4-H), 6.98 (d, 2H, J ) 6.0 Hz, Py), 7.14 (d, 2H,
J ) 6.0 Hz, Py), 7.20-7.35 (m, 10H, Ph), 8.44 (d, 2H, J ) 6.0
Hz, Py), 8.51 (d, 2H, J ) 6.0 Hz, Py); MS (CI, NH3) m/ z 438,
292, 220; HRMS (CI, NH3) calcd for C22H27F3NO3Si [M + H]+
438.1712, found [M + H]+ 438.1735.
C
12H24O3Si: C, 58.97; H, 9.90. Found: C, 58.75; H, 9.67.
1-(4-P yr id yl)-3-(tr im eth ylsilyl)-3-bu ten -1-ol (5g): Rf 0.28
(EtOAc); IR (film) 3205, 3049, 2954, 2901, 1603, 1414, 1248,
1063, 1004 cm-1; 1H NMR (300 MHz, CDCl3) δ 0.00 (s, 9H, Me3-
Si), 2.24 (dd, 1H, J ) 14.0, 10.0 Hz, 2-H), 2.48 (dd, 1H, J ) 14.0,
3.0 Hz, 2-H), 2.77 (br s, 1 H, OH), 4.59 (dd, 1H, J ) 10.0, 3.5
Hz, 1-H), 5.43 (d, 1H, J ) 2.6 Hz, 4-H), 5.58 (s, 1H, 4-H), 7.15
(d, 2H, J ) 5.5 Hz, py), 8.37 (d, 2H, J ) 5.5 Hz, py); 13C NMR
(75 MHz, CDCl3) δ -1.3, 46.5, 70.9, 120.8, 128.9, 148.5, 149.7,
153.3; MS (CI, NH3) m/ z 222, 206, 108; HRMS (CI, NH3) calcd
for C12H20NOSi [M + H]+ 222.1314, found [M + H]+ 222.1322.
Anal. Calcd for C12H19NOSi: C, 65.12; H, 8.66; N, 6.33.
Found: C, 64.83; H, 8.44; N, 6.50.
(4R/S)-4-[(S)-r-Met h oxy-r-(t r iflu or om et h yl)p h en yla ce-
t oxy]-2-(p h en yld im et h ylsilyl)-1-n on en e. 1:1 mixture of
diastereoisomers: Rf 0.70 (4:1 hexanes:Et2O); 1H NMR (300
MHz, CDCl3) δ 0.30 (s, 3H, CH3Si), 0.33 (s, 3H, CH3Si), 0.35 (s,
3H, CH3Si), 0.37 (s, 3H, CH3Si), 0.65-1.50 (m, 22H, 2 × CH3-
(CH2)4), 2.18 (dd, 1H, J ) 14.1, 6.5 Hz, 3-H), 2.25 (dd, 1H, J )
14.1, 6.5 Hz, 3-H), 2.36 (dd, 1H, J ) 14.1, 7.1 Hz, 3-H), 2.46 (dd,
1H, J ) 14.1, 7.1 Hz, 3-H), 3.44 (q, 6H, J ) 1.1 Hz, 2 x CH3O),
5.02 (m, 2H, 2 × 4-H), 5.23 (d, 1H, J ) 2.5 Hz, 1-H), 5.44 (d, 1H,
J ) 2.5 Hz, 1-H), 5.53 (m, 1H, 1-H), 5.65 (m, 1H, 1-H), 7.20-
7.50 (m, 20H, Ph); MS (CI, NH3) m/ z 510, 386; HRMS (CI, NH3)
calcd for C27H39F3NO3Si [M + NH4]+ 510.2651, found [M +
NH4]+ 510.2644.
1-P h en yl-3-(p h en yld im et h ylsilyl)-3-b u t en -1-ol (5h ): Rf
0.26 (4:1 hexanes:Et2O); IR (film) 3403, 3064, 3050, 2956, 2922,
1602, 1492, 1452, 1428, 1251, 1112, 1047 cm-1 1H NMR (300
;
MHz, CDCl3) δ 0.36 (s, 3H, CH3Si), 0.37 (s, 3H, CH3Si), 1.91 (d,
1H, J ) 2.3 Hz, OH), 2.36 (dd, 1H, J ) 14.0, 9.7 Hz, 2-H), 2.52
(ddd, 1H, J ) 14.0, 3.6, 1.0 Hz, 2-H), 4.46 (ddd, 1H, J ) 9.7, 3.6,
2.3 Hz, 1-H), 5.57 (d, 1H, J ) 2.8 Hz, 4-H), 5.78 (m, 1H, 4-H),
7.10-7.25 (m, 5H, Ph), 7.25-7.35 (m, 3H, Ph), 7.45-7.55 (m,
2H, Ph); 13C NMR (75 MHz, CDCl3) δ -2.8, -2.7, 47.1, 72.4,
125.9, 127.4, 128.1, 128.4, 129.4, 130.1, 134.0, 137.8, 144.3, 147.5;
MS (CI, NH3) m/ z 300, 282, 265, 204; HRMS (CI, NH3) calcd
for C18H26NOSi [M + NH4]+ 300.1784, found [M + NH4]+
300.1807. Anal. Calcd for C18H22OSi: C, 76.56; H, 7.86.
Found: C, 76.26; H, 7.66.
(4R/S)-4-[(S)-r-Met h oxy-r-(t r iflu or om et h yl)p h en yla ce-
toxy]-4-p h en yl-2-(p h en yld im eth ylsilyl)-1-bu ten e. 1:1 mix-
1
ture of diastereoisomers: Rf 0.54 (4:1 hexanes:Et2O); H NMR
(300 MHz, CDCl3) δ 0.27 (s, 3H, CH3Si), 0.30 (s, 3H, CH3Si),
0.31 (s, 3H, CH3Si), 0.32 (s, 3H, CH3Si), 2.43 (dd, 1H, J ) 14.6,
5.0 Hz, 3-H), 2.46 (dd, 1H, J ) 14.6, 4.6 Hz, 3-H), 2.64 (dd, 1H,
J ) 14.6, 9.0 Hz, 3-H), 2.68 (dd, 1H, J ) 14.6, 9.3 Hz, 3-H), 3.32