1H), 7.42-7.54 (m, 6H), 7.66-7.76 (m, 4H); 13C NMR (125 MHz,
CDCl3) δ 31.3, 36.0 (d, J ) 70 Hz), 61.8, 66.5, 71.2, 73.1 (d, J )
4.1 Hz), 128.8 (d, J ) 12.3 Hz), 130.4, 130.4, 130.5, 131.0, 131.1,
131.2, 132.0, 132.2, 132.8, 133.0, 133.2 (130.4-133.2, multiple
peaks); 31P NMR (202 MHz, CDCl3) δ 34.6; ESI-MS m/z 355 (M
+ Na); FAB-HRMS calcd for C18H22O4P (M + H) 333.1256, found
333.1254.
(dd, J ) 11.9, 4.6 Hz, 1H), 4.08 (dddd, J ) 11.3, 9.5, 8.0, 3.4 Hz,
1H), 5.00 (dd, J ) 9.5, 4.6 Hz, 1H), 5.22 (br s, 1H), 7.41-7.53
(m, 4H), 7.65-7.76 (m, 4H); 13C NMR (125 MHz, CDCl3) δ 26.9,
32.5 (d, J ) 71 Hz), 62.0, 71.9 (d, J ) 5.1 Hz), 79.1, 80.7 (d, J )
10.4 Hz), 128.5 (d, J ) 12.4 Hz), 128.6 (d, J ) 12.3 Hz), 130.6
(d, J ) 9.3 Hz), 131.0 (d, J ) 9.3 Hz), 131.8-132.7 (multiple
peaks), 133.5 (d, J ) 101 Hz); 31P NMR (202 MHz, CDCl3) δ
29.7; ESI-MS m/z 417 (M + Na); FAB-HRMS calcd for C18H20O6-
PS (M + H) 765.2052, found 395.0718.
The enantiomeric purity of 9 was determined as follows: (R)-
MTPACl (8.3 µL, 44.4 µmol) was added to a solution of
chromatographically purified 9 (7.2 mg, 21.7 µmol), Et3N (30 µL,
215 µmol), and DMAP (4.0 mg, 32.7 µmol) in CH2Cl2 (500 µL),
and the mixture was stirred at room temperature for 20 min.
The mixture was filtrated through a silica gel pad and washed
with MeOH/CHCl3 1:9. The solvent was removed in vacuo. The
enantiomeric purity of 9 was determined by 1H NMR analysis
of the crude mixture.
Gen er a l P r oced u r e for th e SN2 Rea ction by Ca tech ols.
Cs2CO3 (48.3 mg, 148 µmol) was added to a solution of cyclic
sulfate 10 (55.4 mg, 140 µmol) and catechol 11 (X ) H, 23.1 mg,
210 µmol) in CH3CN (1.5 mL) at room temperature and the
mixture was heated to reflux. The mixture was stirred for 1 h
at the same temperature and cooled to room temperature. H2-
SO4 aq (20%; 4 mL) and Et2O (2 mL)-CHCl3 (2 mL) were added
and the mixture was heated to reflux. The mixture was vigor-
ously stirred for 6 h at the same temperature and cooled to room
temperature. The aqueous layer was extracted with CHCl3 and
the combined oraganic layer was washed with brine. Drying over
Na2SO4, followed by concentration, gave a crude oil that was
purified by silica gel column chromatography (MeOH/CHCl3
1:20). The chiral ligand 1a was obtained as a white plate crystal
(44.7 mg, 75%).
Ma jor p r od u ct: colorless oil: [R]24 -11.6 (c 0.80, CHCl3);
D
IR (neat) ν 1754, 1172 cm-1; 1H NMR (500 MHz, CDCl3) δ 1.65
(br d, J ) 15.0 Hz, 1H), 1.84-1.98 (m, 1H), 2.37-2.47 (m, 2H),
3.06 (t, J ) 11.8 Hz, 1H), 3.23 (s, 3H), 3.36 (s, 3H), 3.45 (dd, J
) 11.8, 4.6 Hz, 1H), 4.06 (m, 1H), 5.05 (br d, J ) 9.9 Hz, 1H),
5.58 (br s, 1H), 7.28-7.50 (m, 16H), 7.60-7.67 (m, 4H); 13C NMR
(125 MHz, CDCl3) δ 30.0, 32.5 (d, J ) 72 Hz), 55.3, 55.3, 61.5,
69.3, 69.5 (d, J ) 4.8 Hz), 73.9 (d, J ) 13.2 Hz), 84.2, 84.4, 84.6,
84.8, 85.1 (84.2-85.1, multiple peaks), 123.0 (q, J ) 290 Hz),
126.9, 127.3, 128.2, 128.3, 128.3, 128.4, 128.5, 128.6 (128.2-
128.6, multiple peaks), 129.6, 129.8, 130.6, 130.7, 130.8, 131.1,
131.5, 131.7, 131.7 (130.6-131.7, multiple peaks), 132.8 (d, J )
101 Hz), 133.2 (d, J ) 102 Hz), 165.3, 166.0; 31P NMR (202 MHz,
CDCl3) δ 30.0; 19F NMR (470 MHz, CDCl3) δ -72.7, -71.8; ESI-
MS m/z 787 (M + Na); FAB-HRMS calcd for C38H36F6O8P (M +
H) 765.2052, found 765.2050.
Ch ir a l liga n d 1a : white plate crystal; mp.219-221 °C; [R]23
D
+11.0 (c 1.15, MeOH); IR (film) ν 3188, 1495, 736 cm-1; 1H NMR
(500 MHz, CDCl3) δ 1.87 (qd, J ) 12.5, 4.6 Hz, 1H), 2.08 (dd, J
) 12.5, 4.6 Hz, 1H), 2.70-2.85 (m, 2H), 3.15 (t, J ) 12.5 Hz,
1H), 3.40 (dt, J ) 13.7, 8.9 Hz, 1H), 3.58 (ddd, J ) 12.5, 8.9, 4.6
Hz, 1H), 3.67 (t, J ) 8.9 Hz, 1H), 3.79 (dd, J ) 12.5, 4.6 Hz,
1H), 6.69 (td, J ) 7.5, 1.9 Hz, 1H), 6.87-6.97 (m, 3H), 7.30 (br
s, 1H), 7.41-7.53 (m, 6H), 7.66-7.75 (m, 4H), 8.93 (br s, 1H);
13C NMR (125 MHz, CDCl3) δ 31.6, 35.6 (d, J ) 69.0 Hz), 65.3,
74.7 (d, J ) 5.1 Hz), 75.8, 84.5, 117.0, 119.1, 121.8, 125.0, 128.7
(d, J ) 12.3 Hz), 130.5 (d, J ) 9.3 Hz), 130.6 (d, J ) 97.8 Hz),
131.0 (d, J ) 10.4 Hz), 131.9 (d, J ) 104 Hz), 132.2 (d, J ) 4.1
Hz), 132.4 (d, J ) 4.1 Hz), 145.8, 149.7; 31P NMR (202 MHz,
CDCl3) δ 34.3; ESI-MS m/z 447 (M + Na); FAB-HRMS calcd for
C24H26O5P (M + H) 425.1518, found 425.1517.
Min or p r od u ct: colorless oil: [R]24 +42.3 (c 0.52, CHCl3);
D
IR (neat) ν 1754, 1172 cm-1; 1H NMR (500 MHz, CDCl3) δ 1.81
(br d, J ) 13.4 Hz, 1H), 1.97-2.10 (m, 2H), 2.26 (dt, J ) 13.4,
10.6 Hz, 1H), 3.29-3.27 (m, 4H), 3.35 (s, 3H), 3.61 (dd, J ) 11.6,
4.9 Hz, 1H), 3.93 (q, J ) 10.6 Hz, 1H), 5.00 (dd, J ) 10.6, 2.3
Hz, 1H), 5.64 (br s, 1H), 7.16-7.22 (m, 2H), 7.29-7.52 (m, 18
H); 13C NMR (125 MHz, CDCl3) δ 30.3, 32.1 (d, J ) 72 Hz), 54.9,
55.6, 69.7 (d, J ) 4.8 Hz), 70.1, 73.7 (d, J ) 13.2 Hz), 84.0, 84.2,
84.5, 84.7, 84.9 (84.0-84.9, multiple peaks), 123.0 (q, J ) 290
Hz), 123.0 (q, J ) 290 Hz), 126.8, 127.5, 128.3 (d, J ) 12.0 Hz),
128.5, 128.5, 128.6 (128.5-128.6, multiple peaks), 129.8, 129.8,
130.6, 130.7, 131.0, 131.0, 131.1, 131.5, 131.5, 131.6, 131.6, 131.7,
131.7, 132.3 (129.8-132.3, multiple peaks), 133.6 (d, J ) 102
Hz), 165.6, 166.1; 31P NMR (202 MHz, CDCl3) δ 30.3; 19F NMR
(470 MHz, CDCl3) δ -72.6, -71.9; ESI-MS m/z 787 (M + Na);
FAB-HRMS calcd for C38H36F6O8P (M + H) 765.2052, found
765.2059.
Ch ir a l liga n d 1b: white amorphous; [R]29 +99.0 (c 1.53,
D
1
CHCl3); IR (film) ν 3162, 1513, 1159 cm-1; H NMR (500 MHz,
CDCl3) δ 1.91 (qd, J ) 12.2, 4.6 Hz, 1H), 2.07 (dd, J ) 12.2, 4.6
Hz, 1H), 2.67 (td, J ) 15.3, 10.1 Hz, 1H), 2.82 (br t, J ) 15.3
Hz, 1H), 3.24 (t, J ) 12.2 Hz, 1H), 3.32 (br dd, J ) 10.1, 8.9 Hz,
1H), 3.49 (ddd, J ) 12.2, 8.9, 4.6 Hz, 1H), 3.67 (t, J ) 8.9 Hz,
1H), 3.88 (dd, J ) 12.2, 4.6 Hz, 1H), 6.70-6.78 (m, 2H), 7.43-
7.61 (m, 6H), 7.68-7.77 (m, 4H); 13C NMR (125 MHz, CDCl3) δ
31.4, 36.9 (d, J ) 68.0 Hz), 65.3, 74.7, 75.9, 85.6, 105.5 (d, J )
20.3 Hz), 111.1 (d, J ) 20.4 Hz), 129.0 (d, J ) 12.0 Hz), 129.1
(d, J ) 12.0 Hz), 130.0 (d, J ) 101 Hz), 130.5 (d, J ) 9.6 Hz),
131.0 (d, J ) 9.6 Hz), 131.6 (d, J ) 107 Hz), 132.5, 132.5, 141.0
(dd, J ) 8.4, 3.6 Hz), 142.5 (dd, J ) 241, 13.2 Hz), 146.6 (dd, J
) 9.6, 2.4 Hz), 147.4 (dd, J ) 244, 13.2 Hz); 31P NMR (202 MHz,
CDCl3) δ 34.1; 19F NMR (470 MHz, CDCl3) δ -149.8 (dt, J )
23.0, 11.3 Hz), -142.1 (dt, J ) 20.2, 11.8 Hz); ESI-MS m/z 483
(M + Na); FAB-HRMS calcd for C24H24F2O5P (M + H) 461.1329,
found 461.1322.
4-(D ip h e n y lp h o s p h in o y lm e t h y l)t e t r a h y d r o [1,3,2]-
d ioxa th iolo[4,5-c]p yr a n -2,2-d ioxid e (10). SOCl2 (600 µL, 8.22
mmol) was added to a solution of diol 9 (2.17 g, 6.53 mmol) in
CH2Cl2 (25 mL), and the mixture was stirred for 30 min at room
temperature. The reaction mixture was concentrated, followed
by coevaporation with toluene two times. The resulting crude
cyclic sulfite was dissolved in CCl4 (10 mL)/CH3CN (10 mL)/
H2O (20 mL), and NaIO4 (2.12 g, 9.91 mmol) and RuCl3‚nH2O
(16.1 mg, 77.6 µmol) were added in an ice bath. After the solution
was stirred vigorously for 1 h, H2O was added, and the aqueous
layer was extracted with ethyl acetate. The solvent was removed,
and the residue was dissolved in ethyl acetate. The combined
organic layer was washed with brine, dried over Na2SO4, and
concentrated in vacuo. The crude mixture was purified by silica
gel column chromatography (MeOH/ CHCl3 1:20) to afford 10
Ack n ow led gm en t. Financial support was provided
by RFTF of the J apan Society for the Promotion of
Science and PRESTO of the J apan Science and Tech-
nology Corporation.
Su p p or t in g In for m a t ion Ava ila b le: 1H NMR and 13C
NMR spectra of 1a , 1b, 7, 9, and 10. This material is available
(2.33 g, 90%) as a white powder: [R]24 -41.4 (c 1.32, CHCl3);
D
IR (film) ν 1389, 1210 cm-1; 1H NMR (500 MHz, CDCl3) δ 2.07-
2.18 (m, 2H), 2.56 (ddd, J ) 15.6, 12.2, 8.0 Hz, 1H), 2.74 (ddd,
J ) 15.6, 10.1, 3.4 Hz, 1H), 3.43 (td, J ) 11.9, 3.1 Hz, 1H), 3.71
J O049258O
6130 J . Org. Chem., Vol. 69, No. 18, 2004