Notes
J . Org. Chem., Vol. 65, No. 18, 2000 5861
120.5, 36.4 (J CP ) 2.4 Hz); 31P NMR (D2O) δ 27.7 (t, J PF ) 107.2
Hz); 19F NMR (D2O) δ -43.9 (d, J FP ) -107.2 Hz); IR (KBr) 3064,
1610, 1110, 1038, 606 cm-1; FABMS m/z 339 (M-). Anal. Calcd
for C10H9BrF2O2PSNa‚H2O: C, 31.35; H, 2.89. Found: C, 31.01;
H, 2.65.
cm-1; EIMS m/z 314 (M+); HREIMS m/z calcd for C14H13O2F2-
PS 314.0342, found 314.0392.
S-P r op en yl h yd r ogen d iflu or o(2-n a p h th yl)m eth ylp h os-
p h on oth ioa te 8f: an oil; 1H NMR (CDCl3) δ 12.0 (1H, broad s),
8.08 (1H, s), 7.91-7.89 (3H, m), 7.65-7.58 (3H, m), 5.07 (1H,
dd, J ) 1.1, 16.8 Hz), 4.99 (1H, d, J ) 10.2 Hz), 3.3 (2H, dd, J
) 7.1, 11.6 Hz); 13C NMR (CDCl3) δ 134.2, 132.8 (d, J CP ) 5.5
Hz), 132.3, 128.8 (dt, J CP ) 12.9 Hz), 128.8, 128.1, 127.1, 127.6,
127.3 (dt, J CP ) 178.5 Hz, J CF ) 263.5 Hz), 126.7, 123.2 (t, J CF
) 5.4 Hz), 119.2 (dt, J CP ) 178.5 Hz, J CF ) 265.3 Hz), 118.8,
33.8 (d, J CP ) 2.7 Hz), 31P NMR (CDCl3) δ 38.4 (t, J PF ) 127.5
Hz); 19F NMR (CDCl3) δ -39.2 (d, J FP ) 127.5 Hz); IR (KBr)
3062, 1638, 1241, 1190, 1066, 967, 595 cm-1; EIMS m/z 314 (M+);
HREIMS m/z calcd for C14H13O2F2PS 314.0342, found 314.0356.
Typical Depr otection P r ocedu r e of th e S-Allyl P h osph o-
n oth ioa te. P ota ssiu m d iflu or o(4-m eth ylp h en yl)m eth yl-
p h osp h on oth ia te 19a . A solution of 8a (556 mg, 2.0 mmol),
potassium 2-ethylhexanoate (720 mg, 4.0 mmol), and Pd(PPh3)4
(231 mg, 0.2 mmol) in CH2Cl2 (10 mL) was stirred at 0 °C in the
dark for 4 h. The solvent was evaporated, and the residue was
dissolved in 50% H2O/MeOH (10 mL) and extracted with Et2O.
Evaporation of the aqueous layer gave crude 19a . Column
chromatography of the crude on ODS eluted with water gave
19a in 30% yield: mp > 250 °C; 1H NMR (D2O) δ 7.52 (2H, d, J
) 7.9 Hz), 7.27 (2H, d, J ) 7.9 Hz), 2.34 (3H, s); 13C NMR (D2O)
δ 147.8, 140.2 (dt, J CP ) 12.7 Hz, J CF ) 22.9 Hz), 136.2, 134.2
(t, J CF ) 6.3 Hz), 130.2 (dt, J CP ) 144.1 Hz, J CF ) 265.5 Hz),
28.2; 31P NMR (D2O) δ 45.9 (t, J PF ) 99.0 Hz); 19F NMR (D2O)
δ -40.5 (d, J FP ) 99.9 Hz); IR (KBr) 1144, 1081, 1016, 653, 622
cm-1; FABMS m/z 353 (MK+), 315 (MH+); HRMS (FAB) m/z
calcd for C8H7O2F2K3PS (MK+) 352.8784, found 352.8789. Anal.
Calcd for C8H7O2F2K2PS‚2H2O: C, 27.42; H, 3.17. Found: C,
27.51; H, 3.26.
Sod iu m S-p r op en yl [1,1′-bip h en yl]-3-yl(d iflu or o)m eth -
ylp h osp h on oth ioa te 18d : mp ) 239-241 °C; 1H NMR (D2O)
δ 7.77 (1H, s), 7.59-7.57 (1H, d, J ) 7.6 Hz), 7.27-7.08 (4H,
m), 7.03-6.95 (3H, m), 5.50-5.34 (1H, m), 4.74 (1H, d, J ) 16.9
Hz), 4.63 (1H, d, J ) 9.9 Hz), 3.39 (2H, dd, J ) 7.0, 14.1 Hz);
13C NMR (D2O) δ 142.6, 142.3, 136.8 (dt, J CP ) 21.5 Hz, J CF
)
43.3 Hz), 136.5, 136.4, 131.3, 131.0, 130.8, 129.8, 129.2, 128.3,
127.5, 123.2 (dt, J CP ) 159.9 Hz, J CF ) 265.9 Hz), 119.9, 36.5
(d, J CP ) 2.4 Hz); 31P NMR (D2O) δ 27.7 (t, J PF ) 107.2 Hz); 19
F
NMR (D2O) δ -43.9 (d, J FP ) 107.2 Hz); IR (KBr) 3064, 1110,
1038, 606 cm-1; FABMS m/z 339 (M-). Anal. Calcd for C16H14O2F2-
PSNa: C, 53.04; H, 3.89. Found: C, 52.98; H, 4.12.
Sodiu m S-pr open yl diflu or o(1-n aph th yl)m eth ylph osph o-
n oth ioa te 18e: mp ) 245-247 °C; 1H NMR (400 MHz, D2O) δ
8.49 (1H, d, J ) 8.0 Hz), 8.07 (1H, d, J ) 8.2 Hz), 7.99 (1H, J )
7.3 Hz), 7.87 (1H, d, J ) 7.4 Hz), 7.63-7.60 (3H, m), 5.83-5.73
(1H, m), 5.14 (1H, dd, J ) 1.3, 17.0 Hz), 5.05 (1H, d with small
splits, J ) 10.0 Hz), 3.24 (2H, dd, J ) 7.2, 9.8 Hz); 13C NMR
(D2O) δ 137.2, 136.6, 134.4, 133.7, 132.5, 131.9 (dt, J CP ) 12.6
Hz, J CF ) 20.1 Hz), 131.5, 129.8 (dt, J CP ) 1.9 Hz, J CF ) 9.8
Hz), 129.5, 129.0 (two carbons), 127.6, 125.6 (dt, J CP ) 158.8
Hz, J CF ) 266.2 Hz); 31P NMR (D2O) δ 28.6 (t, J PF ) 108.1 Hz);
19F NMR (D2O) δ -36.2 (d, J FP ) 108.1 Hz); IR (KBr) 3100, 1512,
1256, 1112, 613 cm-1; FABMS m/z 313 (M-). Anal. Calcd for
C
14H12F2O2PSNa H2O: C, 47.46; H, 3.98. Found: C, 47.34; H,
3.61.
Sodiu m S-pr open yl diflu or o(2-n aph th yl)m eth ylph osph o-
1
n oth ioa te 18f: mp ) 245-248 °C; H NMR (D2O) δ 8.07 (1H,
s), 7.68 (2H, s), 7.64 (1H, d with small splits, J ) 9.0 Hz), 7.51
(1H, d, with small splits, J ) 9.0 Hz), 7.18 (2H, m), 5.54 (1H,
m), 4.83 (1H, dd, J ) 1.1, 17.0 Hz), 4.76 (1H, J ) 10.0 Hz), 3.00
(2H, dd, J ) 8.5, 8.5 Hz); 13C NMR (D2O) δ 136.9, (d, J CP ) 4.8
Hz), 136.2, 130.7, 130.2, 129.9, 129.3 (two carbons), 126.0 (t, J CF
) 5.1 Hz), 123.7 (dt, J CP ) 160.6 Hz, J CF ) 265.5 Hz), 120.2,
36.4 (d, J CP ) 2.9 Hz); 31P NMR (D2O) δ 28.2 (d, J PF ) 108.9
Hz); 19F NMR (D2O) -43.0 (d, J FP ) 108.9 Hz); IR (KBr) 3150,
1604, 1250, 1112, 1040, 590 cm-1; FABMS m/z 313 (M-). Anal.
Calcd for C14H12F2O2PSNa‚1/3H2O: C, 49.03; H, 3.92. Found: C,
49.31; H, 3.91.
P ota ssiu m [1,1′-bip h en yl]-3-yl(d iflu or o)m eth ylp h osp h o-
n oth ioa te 19d : yield 25%; mp > 250 °C; 1H NMR (D2O) δ 7.76
(1H, s), 7.60-7.53 (3H, m), 7.47 (1H, d, J ) 7.7 Hz), 7.39-7.30
(3H, m), 7.24 (1H, t, J ) 7.4 Hz); 13C NMR (D2O) δ 147.8, 147.6,
144.1 (dt, J CP ) 12.5 Hz, J CF ) 22.7 Hz), 136.8, 136.2, 135.5,
134.7, 133.3 (t, J CF ) 6.5 Hz), 132.8 (t, J CF ) 6.6 Hz), 129.8 (dt,
J CP ) 143.4 Hz, J CF ) 266.2 Hz); 31P NMR (D2O) δ 45.9 (t, J PF
) 98.0 Hz); 19F NMR (D2O) δ -41.3 (d, J FP ) 98.0 Hz); IR (KBr)
1129, 1021, 628, cm-1; FABMS m/z 415 (MK+). Anal. Calcd for
C13H9O2F2K2PS‚2H2O: C, 37.85; H, 3.18. Found: C,37.42; H,
3.01.
S-P r op en yl h yd r ogen d iflu or o(4-m et h yp h en yl)m et h -
ylp h osp h on oth ioa te 8a : an oil; H NMR (CDCl3) δ 11.3 (1H,
P ota ssiu m d iflu or o(1-n a p h th yl)m eth ylp h osp h on oth io-
a te 19e: yield 29%; mp > 250 °C; 1H NMR (D2O) d 8.60 (1H, d,
J ) 8.7 Hz), 7.92 (1H, d, J ) 7.4 Hz), 7.68 (1H, d, J ) 8.3 Hz),
7.59 (1H, d, J ) 8.1 Hz), 7.52-7.40 (2H, m), 7.31 (1H, t, J ) 7.4
1
broad s), 7.47 (2H, J ) 7.8 Hz), 7.23 (2H, d, J ) 7.8 Hz), 5.84-
5.71 (1H, m), 5.20 (1H, dd, J ) 1.1, 16.9 Hz), 5.11 (1H, d, J )
10.0 Hz) 3.41 (2H, dd, J ) 10.0 Hz), 2.39 (3H, s); 13C NMR
(CDCl3) δ 141.1, 132.9 (d, J CP ) 5.6 Hz), 128.4 (s), 128.4 (dt, J CP
) 14.0 Hz, J CF ) 22.2 Hz), 126.7, 126.2, 119.4 (dt, J CP ) 179.1
Hz, J CF ) 265.2 Hz), 118.9, 33.7 (d, J CP ) 2.5 Hz); 31P NMR
(CDCl3) δ 39.4 (t, J PF ) 130.4 Hz), 19F NMR (CDCl3) δ -45.6 (d,
J FP ) 130.4 Hz); IR (film) 2926, 1616, 1514, 1409, 1262, 598
cm-1; EIMS m/z 278 (M+); HREIMS m/z calcd for C11H13O2F2-
PS 278.0342, found 278.0352.
Hz); 13C NMR (D2O) δ 131.8, 129.7 (dt, J CP ) 11.7 Hz, J CF
)
20.7 Hz), 128.8, 128.3, 126.6, 125.4, 125.3 (t, J CF ) 9.7 Hz), 124.3,
124.0, 122.8, 122.6 (dt, J CP ) 141.4 Hz, J CF ) 266.9 Hz); 31P
NMR (D2O) δ 46.7 (t, J PF ) 97.1 Hz); 19F NMR (D2O) δ -33.1
(d, J FP ) 97.1 Hz); IR (KBr) 1596, 1499, 1254, 1141, 1105, 1008
cm-1; FABMS m/z 389 (MK+). Anal. Calcd for C11H7O2F2K2PS‚
5/2H2O: C, 33.40; H, 3.06. Found: C, 33.33; H, 2.98.
P ota ssiu m d iflu or o(2-n a p h th yl)m eth ylp h osp h on oth io-
a te 19f: yield 23%; mp > 250 °C; 1H NMR (D2O) δ 8.15 (1H, s),
8.01-7.89 (3H, m), 7.74 (1H, d, J ) 8.5 Hz), 7.59-7.52 (2H, m);
13C NMR (D2O) δ 133.6, 133.6 (dt, J CP ) 11.8 Hz, J CF ) 22.3
Hz), 132.4, 128.9, 128.0, 127.8, 127.5, 127.1, 126.6 (t, J CF ) 6.8
S-P r op en yl h yd r ogen [1,1′-bip h en yl]-3-yl(d iflu or o)m -
eth ylp h osp h on oth ioa te 8d : an oil; 1H NMR (CDCl3) δ 11.6
(1H, broad s), 7.80-7.61 (4H, m), 7.59-7.39 (4H, m), 5.90-5.75
(1H, m), 5.23 (1H, d, J ) 16.9 Hz), 5.13 (1H, d, J ) 10.0 Hz); 13
C
NMR (CDCl3) δ 141.3, 140.0, 132.7, 132.0 (dt, J CP ) 13.7 Hz,
J CF ) 21.8 Hz), 129.5, 128.8, 128.6, 127.7, 127.1, 126.9, 125.6,
Hz), 124.4 (t, J CF ) 5.7 Hz), 122.8 (dt, J CP ) 143.4 Hz, J CF
)
266.1 Hz); 31P NMR (D2O) δ 46.0 (t, J PF ) 98.2 Hz); 19F NMR
(D2O) δ -40.7 (d, J FP ) 98.2 Hz); IR (KBr) 1125, 1016, 636 cm-1
FABMS m/z 389 (MK+), 351 (MH+). Anal. Calcd for C11H7O2F2K2-
PS‚3H2O: C, 32.67; H, 3.24. Found: C, 32.21; H, 2.74.
;
125.4, 119.1 (dt, J CP ) 176.7 Hz, J CF ) 265.7 Hz), 33.9 (d, J CP
)
2.2 Hz); 31P NMR (CDCl3) δ 38.8 (t, J PF ) 126.1 Hz); 19F NMR
(CDCl3) δ -46.0 (d, J PF ) 126.1 Hz); IR (KBr) 3445, 3050, 1600,
1480, 1224, 756, 701 cm-1; EIMS m/z 340 (M+); HREIMS m/z
calcd for C16H15O2F2PS 340.0498, found 340.0495.
Ack n ow led gm en t. This work was supported in part
by Grant-in-Aid for Scientific Research (C) from the
Ministry of Education, Science, Sports and Culture of
the J apanese Government.
S-P r op en yl h yd r ogen d iflu or o(1-n a p h th yl)m eth ylp h os-
p h on oth ioa te 8e: an oil; 1H NMR (CDCl3) δ 12.0 (1H, broad
s), 8.52 (1H, d, J ) 9.2 Hz), 7.91 (1H, d, J ) 8.1 Hz), 7.87-7.86
(1H, m), 5.08 (1H, d, J ) 16.9 Hz), 5.01 (1H, d, J ) 9.9 Hz), 3.26
(2H, dd, J ) 7.2, 11.3 Hz); 13C NMR (CDCl3) δ 134.0, 132.7 (d,
J CP ) 5.5 Hz), 132.2, 130.1, 128.5, 127-126.9 (two carbons, m),
Su p p or tin g In for m a tion Ava ila ble: Experimental pro-
cedure and complete characterization data for new compounds
7a -f and 13b-d . This material is available free of charge via
the Internet at http://pubs.acs.org.
126.8, 126.4-125.8 (two carbons, m), 124.3, 120.8 (dt, J CP
)
176.9 Hz, J CF ) 266.1 Hz), 118.9, 33.7 (d, J CP ) 2.4 Hz); 31P
NMR (CDCl3) δ 40.0 (t, J PF ) 127.6 Hz); 19F NMR (CDCl3) δ
-45.6 (d, J CF ) 127.6 Hz); IR (film) 3273, 3059, 1513, 1244, 772
J O000563T