260 J . Org. Chem., Vol. 64, No. 1, 1999
Itoh et al.
4.12 (1H, dt, J ) 8.5, 3.6 Hz); 13C NMR (50 MHz, CDCl3,) 7.53
J ) 299.4 Hz); IR (neat) 2935, 2858, 1826, 1454, 1171 cm-1
.
(d, J C-F ) 7.6 Hz), 13.64, 22.20, 27.02, 32.88, 42.78 (t, J C-F
)
Anal. Calcd for C11H13F5O2: C, 48.54; H, 4.81. Found: C, 48.61;
H, 4.77.
20.5 Hz), 82.93 (d, J C-F ) 8.0 Hz), 115.70 (dd, J C-F ) 259.6,
251.1 Hz), 165.28 (dd, J C-F ) 33.9, 31.8 Hz); 19F NMR (188
MHz, CDCl3) 41.23 (1F, dd, J ) 274.7, 21.0 Hz), 47.30 (1F,
dd, J ) 275.0, 13.2 Hz); IR (neat) 2950, 1810, 1460, 1320, 1210,
cm-1. Anal. Calcd for C9H14F2O2: C, 56.24; H, 7.34. Found:
C, 56.69; H, 7.61.
(3S*,4S*)-3-(Diflu or om et h yl)-2,2,3-t r iflu or od eca n -4-
olid e (1k ): bp 70 °C/2.5 mmHg (Kugelrohr); Rf 0.58 (hexane/
ethyl acetate ) 10:1); 1H NMR (200 MHz, CDCl3) 0.90 (3H, t,
J ) 6.8 Hz), 1.25-1.92 (10H, m), 4.79 (1H, ddd, J ) 18.6, 8.8,
4.3 Hz), 6.15 (1H, dt, J ) 52.5, 6.7 Hz); 13C NMR (50 MHz,
CDCl3) 13.95, 22.43, 24.91, 27.97 (d, J C-F ) 7.0 Hz), 28.62,
31.37, 78.59 (d, J C-F ) 21.7 Hz), 109.85 (ddt, J C-F ) 248.0,
29.5, 2.7 Hz), 160.75 (dd, J C-F ) 33.1, 30.7 Hz); 19F NMR (188
MHz, CDCl3) -38.84 to -38.79 (1F, m), 28.72 (1F, ddt, J )
311.3, 51.9, 9.2 Hz), 30.70 (1F, ddt, J ) 308.3, 51.2, 6.4 Hz),
36.20 (1F, dd, J ) 294.4, 8.8 Hz), 38.55 (1F, ddd, J ) 297.1,
17.0, 9.2 Hz); IR (neat) 2931, 2862, 1826, 1468, 1265, 1169
cm-1. Anal. Calcd for C11H15F5O2: C, 48.18; H,5.51 Found: C,
48.00; H, 5.59.
(3R*,4S*)-2,2-Diflu or o-7,3-d im eth yl-6-octen -4-olide (1f):
bp 75 °C/2.2 mmHg (Kugelrohr); Rf 0.39 (hexane/ethyl acetate
) 10:1); 1H NMR (200 MHz, CDCl3) 1.18 (3H, dd, J ) 6.9, 1.2
Hz), 1.61 (3H, s), 1.71 (3H, s), 2.22-2.59 (3H, m), 4.17 (1H,
dt, J ) 8.8, 5.5 Hz), 5.05-5.15 (1H, m); 13C NMR (50 MHz,
CDCl3,) 7.71 (d, J C-F ) 7.7 Hz), 17.93, 25.75, 31.00, 41.70 (t,
J C-F ) 20.6 Hz), 82.53 (d, J C-F ) 8.0 Hz), 115.73 (dd, J C-F
)
259.6, 251.1 Hz), 115.94, 137.19, 165.27 (dd, J C-F ) 34.0, 32.0
Hz); 19F NMR (188 MHz, CDCl3) 41.65 (1F, dd, J ) 274.7, 21.0
Hz), 47.38 (1F, dd, J ) 274.9, 12.6 Hz); IR (neat) 2922, 1811,
1460, 1337, 1213, cm-1. Anal. Calcd for C10H14F2O2: C, 58.81;
H, 6.91. Found: C, 57.44; H, 7.03.
La ctol 4a (m ixtu r e of d ia ster eom er s): bp 100 °C/4.0
1
mmHg (Kugelrohr); Rf 0.63 (hexane/ethyl acetate ) 7:1); H
NMR (200 MHz, CDCl3) 0.12-0.13 (9H, m), 0.96-1.03 (3H,
m) 1.76-1.88 (2H, m), 1.88-2.35 (1H, m), 2.48-2.85 (2H, m),
3.58 (0.5H, dt, J ) 4.6, 4.1 Hz), 3.85 (0.5H, dd, J ) 12.7, 6.5
Hz), 5.02 (0.5H, d, J ) 6.9 Hz), 5.17 (0.5H, d, J ) 6.5 Hz),
7.08-7.24 (5H, m); 13C NMR (50 MHz, CDCl3) 0.23, 0.39, 7.45
(d, J C-F ) 7.3 Hz), 11.67 (d, J C-F ) 7.7 Hz), 31.75, 31.85, 36.21,
37.39, 40.39 (t, J C-F ) 21.3 Hz), 43.91 (t, J C-F ) 23.4 Hz), 81.96
(d, J C-F )8.3 Hz), 83.12-83.27 (m), 95.60 (dd, J C-F ) 41.1,
26.2 Hz), 97.12 (dd, J C-f ) 43.7, 23.8 Hz), 125.94, 126.45 (dd,
J C-F ) 261.6, 247.5 Hz), 128.35, 128.41, 141.50, 141.64; 19F
NMR (188 MHz, CDCl3) 36.79 (0.5F, ddd, J ) 229.4, 23.3, 6.8
Hz), 38.46 (0.5F, d, J ) 233.1 Hz), 38.74 (0.5F, dd, J ) 229.4,
10.4 Hz), 61.15 (0.5F, ddd, J ) 232.9, 24.3, 6.4 Hz); IR (neat)
2950, 1600, 1450, 1365, 1250 cm-1. Anal. Calcd for C16H24F2O2-
Si: C, 61.12; H, 7.69. Found: C, 61.55; H, 7.65.
cis-(3S*,4S*)-3-(Diflu or om eth yl)-2,2-d iflu or o-3-((m eth -
oxyeth oxy)m eth oxyh exa n -4-olid e (1g): bp 90 °C/3.8 mmHg
(Kugelrohr); Rf 0.32 (hexane/ethyl acetate ) 4:1); 1H NMR (200
MHz, CDCl3) 1.08 (3H, t, J ) 16.5 Hz), 1.60-1.96 (2H, m),
3.38 (3H, s), 3.55-3.95 (4H, m), 4.71-4.74 (1H, m), 4.93-5.24
(2H, m), 6.52 (1H, t, J ) 53.6 Hz); 13C NMR (50 MHz, CDCl3,)
9.56, 22.74, 58.88, 68.23, 71.19, 77.19-79.00 (m), 80.66 (dd,
J C-F ) 6.8 Hz, 4.4 Hz), 93.30 (d, J C-F ) 4.8 Hz), 112.21 (ddt,
J C-F ) 250.6, 247.1, 3.6 Hz), 162.10 (t, J C-F ) 31.0 Hz); 19F
NMR (188 MHz, CDCl3) 29.19 (1F, ddd, J ) 305.5, 54.3, 7.1
Hz), 31.30 (1F, ddd, J ) 305.9, 53.4, 12.2 Hz), 40.43 (1F, dd,
J ) 288.9, 12.2 Hz), 47.48 (1F, dd, J ) 289.3, 6.8 Hz); IR (neat)
2939, 1820, 1462, 1236, 1163 cm-1
11H16F4O5: C, 43.43; H, 5.30. Found: C, 43.47; H, 5.46.
t r a n s-(3S *,4R *)-3-(Diflu or om e t h yl)-2,2-d iflu or o-3-
. Anal. Calcd for
C
La ctol 4b (m ixtu r e of d ia ster eom er s): bp 50 °C/45
1
((m eth oxyeth oxy)m eth oxy)h exa n -4-olid e (1g): bp 90 °C/
3.8 mmHg (Kugelrohr); Rf 0.26 (hexane/ethyl acetate ) 4:1);
1H NMR (200 MHz, CDCl3) 1.14 (3H, t, J ) 7.4 Hz), 1.81-
2.05 (2H, m), 3.38 (3H, s), 3.52-3.57 (2H, m), 3.66-3.74 (1H,
m), 3.84-3.93 (1H, m), 4.57 (1H, dd, J ) 9.8, 4.3 Hz), 4.98
(1H, d, J ) 8.0 Hz), 5.18 (1H, d, J ) 7.9 Hz), 6.32 (1H, t, J )
52.7 Hz); 13C NMR (50 MHz, CDCl3,) 10.59, 22.53, 58.88, 68.33,
77.19-79.00 (m), 83.39 (d, J C-F ) 2.3 Hz), 93.06, 113.05 (tt,
J C-F ) 249.8, 3.7 Hz), 161.91 (t, J C-F ) 30.9 Hz); 19F NMR
(188 MHz, CDCl3) 31.27 (2F, dd, J ) 51.9, 6.8 Hz), 39.71 (1F,
dd, J ) 284.9, 6.8 Hz), 41.30 (1F, dd, J ) 285.4, 6.8 Hz); IR
mmHg (Kugelrohr); Rf 0.62 (hexane/ethyl acetate ) 7:1); H
NMR (200 MHz, CDCl3) 0.19 (9H, s), 1.08-1.16 (3H, m), 2.35-
2.60 (1H, m), 3.49-3.80 (1H, m), 4.15-4.25 (1H, m), 5.08-
5.19 (1H, m); 13C NMR (50 MHz, CDCl3) -0.01, -0.04, 7.78-
8.06 (m) 12.13 (dd, J C-F ) 7.4, 4.4 Hz), 35.67 (dt, J C-F ) 37.2,
22.3 Hz), 37.85 (dd, J C-F ) 24.4, 22.2 Hz), 70.98-72.31 (m),
72.23 (t, J C-F ) 3.8 Hz), 96.05(dd, J C-F ) 37.9, 29.2 Hz), 96.90
(dd, J C-F ) 43.7, 24.3 Hz), 125.45 (dd, J C-F ) 261.9, 255.3 Hz),
126.08 (dd, J C-F ) 266.1, 245.8 Hz); 19F NMR (188 MHz,
CDCl3) 36.18 (0.5F, d, J ) 233.8 Hz), 36.83 (0.5F, d, 20.0 Hz),
37.04 (0.5F, dd, J ) 20.0, 4.9 Hz), 59.09 (0.5 F, ddd, J ) 233.9,
23.2, 6.6 Hz); IR (neat) 2975, 1460, 1255, 1040 cm-1. Anal.
Calcd for C8H16F2O2Si: C, 45.69; H, 7.67. Found: C, 45.78; H,
7.68.
(neat) 2941, 1823, 1462, 1096 cm-1
11H16F4O5: C, 43.43; H, 5.30. Found: C, 43.54; H, 5.28.
(3S*,4S*)-3-(Diflu or om eth yl)-2,2-d iflu or o-3-((m eth oxy-
. Anal. Calcd for
C
eth oxy)m eth oxy)-3-m eth ylh exa n -4-olid e (1h ): bp 70 °C/
5.0 mmHg (Kugelrohr); Rf 0.40 (hexane/ethyl acetate ) 4:1);
1H NMR (200 MHz, CDCl3) 0.98 (3H, d, J ) 6.6 Hz), 1.04 (3H,
d, J ) 6.8 Hz), 2.09-2.26 (1H, m), 3.34 (3H, s), 3.51 (2H, t, J
) 4.0 Hz), 3.57-3.70 (1H, m), 3.82-3.93 (1H, m), 4.53 (1H, d,
J ) 6.6 Hz), 4.92 (1H, d, J ) 8.0 Hz), 5.19 (1H, d, J ) 9.4 Hz),
6.51 (1H, t, J ) 53.6 Hz); 13C NMR (50 MHz, CDCl3,) 17.39,
19.44, 28.08, 58.89, 68.30, 71.18, 78.00-79.58 (m), 83.58 (dd,
J ) 7.3, 3.8 Hz), 93.27 (d, J ) 5.3 Hz), 112.39 (t, J ) 248.1
Hz), 114.21 (dd, J ) 250.3, 246.2 Hz), 162.09 (t, J ) 31.2 Hz);
19F NMR(188 MHz, CDCl3) 31.24 (1F, d, J ) 51.9 Hz), 31.36
(1F, dd, J ) 63.6, 11.9 Hz), 41.39 (1F, ddd, J ) 289.9, 10.0,
6.1 Hz), 48.01 (1F, d, J ) 289.9 Hz); IR (neat) 2947, 1809, 1475,
1398, 1371, 1237 cm-1. Anal. Calcd for C12H18F4O5: C, 45.29;
H, 5.70. Found: C, 45.33; H, 5.81.
(3S*,4S*)-4-Cycloh exyl-3-(d iflu or om eth yl)-2,2,2-tr iflu o-
r obu ta n -4-olid e (1j): bp 60 °C/4.5 mmHg (Kugelrohr); Rf 0.44
hexane/ethyl acetate ) 10:1); 1H NMR (200 MHz, CDCl3) 1.12-
1.44 (5H, m), 1.68-2.03 (6H, m), 4.57 (1H, dd, J ) 17.6, 7.2
Hz), 6.16 (1H, dt, J ) 53.0, 5.0 Hz,); 13C NMR (50 MHz, CDCl3)
25.20, 25.41, 25.65, 27.81, 28.90, 37.23 (d, J ) 3.9 Hz), 81.92
(d, J ) 21.2 Hz), 91.59 (ddt, J ) 207.1, 26.0, 17.4 Hz), 110.54
(ddt, J ) 251.1, 34.9, 3.4 Hz), 160.81 (t, J ) 31.1 Hz); 19F NMR
(188 MHz, CDCl3) -35.65 to -35.20 (1F, m), 29.01 (1F, ddt, J
) 311.3, 51.9, 12.2 Hz), 31.86 (1F, ddt, J ) 308.6 Hz, 57.7,
11.9 Hz), 37.13 (1F, ddt, J ) 298.8, 13.6, 7.5 Hz), 40.27 (1F, d,
La ctol 4c (m ixtu r e) of d ia ster eom er s: bp 90 °C/2.6
mmHg (Kugelrohr); Rf 0.63 (hexane/ethyl acetate ) 7:1); H
1
NMR (200 MHz, CDCl3) 0.10 (3H, s), 0.22 (6H, s) 2.62-3.12
(3H, m), 3.65-4.11 (2H, m), 5.12 (0.5H, d, J ) 5.8 Hz), 5.21
(0.5H, d, J ) 6.9 Hz); 13C NMR (50 MHz, CDCl3) -0.01, 30.73
(d, J C-F ) 6.2 Hz), 33.42 (dd, J C-F ) 6.7, 3.7 Hz), 41.77 (t,
J C-F ) 21.2 Hz), 44.42 (dd, J C-F ) 23.3, 21.0 Hz), 69.99 (d,
J C-F ) 7.9 Hz), 70.39 (t, J C-F ) 3.7 Hz), 96.28 (dd, J C-F ) 39.3,
27.2 Hz), 97.10 (dd, J C-F ) 40.9, 23.6 Hz), 125.23 (dd, J C-F
)
262.1, 248.6 Hz), 126.47, 126.53, 128.56, 128.61, 138.48,
138.65; 19F NMR (188 MHz, CDCl3) 37.97 (0.5F, d, J ) 233.4
Hz), 38.29 (0.5F, dd, J ) 230.4, 10.9 Hz), 39.91 (0.5F, ddd, J
) 230.4, 20.2 Hz, 5.6 Hz), 60.31 (0.5 F, ddd, J ) 234.7, 22.8,
6.8 Hz); IR (neat) 2950, 1600, 1450, 1365, 1250 cm-1. Anal.
Calcd for C14H20F2O2Si: C, 58.71; H, 7.04. Found: C, 58.89;
H, 7.02.
La ctol 4d (m ixtu r e of d ia ster eom er s): bp 60 °C/7.5
mmHg (Kugelrohr); Rf 0.49 (hexane/ethyl acetate ) 10:1); 1H
NMR (200 MHz, CDCl3) 0.17 (4.5 H, s), 0.18 (4.5 H, s), 0.84-
0.95 (3H, m), 1.03-1.09 (3H, m), 1.79-1.98 (1H, m), 1.98-
2.43 (1H, m), 3.62-3.71 (0.5H, m), 3.86 (0.5 H, t, J ) 9.5 Hz),
4.01-4.10 (0.5H, m), 4.20 (0.5H, t, J ) 8.8 Hz), 5.05 (0.5H,
dd, J ) 7.3, 1.9 Hz), 5.21 (0.5H, d, J ) 7.3 Hz); 13C NMR (50
MHz, CDCl3) -0.10, 20.45, 20.62, 21.09, 21.45, 25.93, 26.02,
46.36 (t, J C-F ) 20.6 Hz), 51.01 (t, J C-F ) 22.1 Hz), 69.28 (dd,
J C-F ) 4.6, 2.2 Hz), 69.95 (d, J C-F ) 9.8 Hz), 96.79 (dd, J C-F
)