Zhang et al.
TABLE 3. Dep en d en ce of th e Dia ster eoselectivity on
th e Ca ta lyts
(23), 71 (51), 59 (16), 45 (25), 27 (4). Anal. Calcd for
C20H22O2S: C, 73.59; H, 6.79. Found: C, 73.45; H, 6.91.
Meth yl 2-(p-p h en ylp h en yl)-2-((2-m eth ylp h en yl)th io)-
4-p en ten oa te (3, Ar ) p-P h C6H4, Ar ′ ) 2-CH3C6H4): HPLC
entry
catal
diastereomeric ratio of 17a
1
2
3
4
5
Rh2(OAc)4
31:69
36:64
36:64
39:61
37:63
(254 nm), 90:10 hexane/2-propanol, tR ) 16.233 min, tR
)
4
22.340 min; mp 73-75 °C; IR (KBr) 3065 (m), 1727 (s); 1H
NMR (200 MHz, CDCl3) δ 2.19 (s, 3H), 2.94-3.00 (m, 2H), 3.71
(s, 3H), 5.01-5.12 (m, 2H), 5.91-6.0 (m, 1H), 7.15-7.62 (m,
13H); 13C NMR (50 MHz, CDCl3) δ 20.73, 41.21, 52.47, 64.32,
118.76, 125.77, 126.52, 126.90, 127.33, 127.87, 128.69, 129.21,
130.19, 130.32, 133.15, 137.56, 138.63, 140.09, 140.27, 143.99,
172.21; MS (m/z, relative intensity) 388 (M+, 3), 329 (1.5), 287
(1), 266 (26), 265.2 (100), 233 (24), 225 (2), 205 (91), 197 (62),
179 (16), 165 (14), 152 (10), 123 (11), 115 (4.5), 84 (33), 71 (30),
59 (39), 49 (32), 35 (4). Anal. Calcd for C25H24O2S: C, 77.29;
H, 6.23. Found: C, 77.18; H, 6.14.
Meth yl 2-(p-br om op h en yl)-2-((2-m eth ylp h en yl)th io)-4-
p en ten oa te (3, Ar ) p-Br C6H4, Ar ′ ) 2-CH3C6H4): HPLC
(254 nm), 99:1 hexane/2-propanol, tR ) 18.533 min, tR ) 24.216
min; mp 70-72 °C; IR (KBr) 1731 (s); 1H NMR (200 MHz,
CDCl3) δ 2.20 (s, 3H), 2.86-2.93 (m, 2H), 3.66 (s, 3H), 5.04-
5.09 (m, 2H), 5.85-5.96 (m, 1H), 7.12-7.41 (m, 8H); 13C NMR
(50 MHz, CDCl3) δ 20.80, 41.55, 52.48, 63.89, 119.02, 121.44,
125.91, 129.38, 129.41, 129.45, 130.07, 130.45, 130.99, 132.78,
137.42, 138.76, 143.84, 171.75; MS (m/z, relative intensity) 392
[(M + 1)+, 11]], 351 (3), 333 (3), 289 (3), 269 (64), 267 (62), 241
(2), 235 (16), 210 (6), 199 (43), 183 (6), 169 (3), 155 (3), 144
(8), 128.2 (100), 115 (7), 91 (16), 77 (22), 71 (78), 59 (41), 39
(12), 27 (5). Anal. Calcd for C19H19O2SBr: C, 58.32; H, 4.89.
Found: C, 58.32; H, 5.07.
Meth yl 2-ph en yl-2-((2-m eth ylph en yl)th io)-1-pen ten oate
(3, Ar ) C6H5, Ar ′ ) 2-CH3C6H4): HPLC (254 nm), 90:10
hexane/2-propanol, tR ) 15.218 min, tR ) 19.570 min; mp 66-
67 °C; IR (KBr) 3059 (m), 1731 (s); 1H NMR (200 MHz, CDCl3)
δ 2.17 (s, 3H), 2.93-2.95 (m, 2H), 3.67 (s, 3H), 4.97-5.06 (m,
2H), 5.89-5.99 (m, 1H), 6.99-7.25 (m, 9H); 13C NMR (50 MHz,
CDCl3) δ 20.65, 41.16, 52.21, 64.47, 118.62, 125.68, 127.33,
127.88, 129.12, 130.23, 133.14, 137.48, 139.61, 143.93, 172.22;
MS (m/z, relative intensity) 312 (M+, 15), 271 (5), 253 (4), 211
(7), 189 (56), 178 (3), 157 (28), 149 (3), 129.1 (100), 121 (61),
115 (16.5), 103 (10), 91 (26), 71 (52), 59 (19), 51 (11), 45 (17),
27 (5). Anal. Calcd for C19H20O2S: C, 73.04; H, 6.45. Found:
C, 73.00; H, 6.62.
Meth yl 2-p h en yl-2-((2,6-d im eth ylp h en yl)th io)-1-p en -
ten oa te (3, Ar ) C6H5, Ar ′ ) 2,6-(CH3)2C6H3): HPLC (254
nm), 90:10 hexane/2-propanol, tR ) 7.553 min, tR ) 8.253 min;
mp 66-68 °C; IR (KBr) 3059 (m), 1730 (s); 1H NMR (200 MHz,
CDCl3) δ 2.35 (s, 6H), 2.87-3.05 (m, 2H), 3.45 (s, 3H), 4.9-
5.00 (m, 2H), 5.58-5.72 (m, 1H), 7.02-7.39 (m, 8H); 13C NMR
(50 MHz, CDCl3) δ 22.268, 30.358, 43.912, 51.501, 64.235,
118.345, 126.83, 127.232, 127.581, 127.763, 129.069, 130.344,
132.810, 139.329, 145.848, 171.363; MS (m/z, relative intensity)
326 (M+, 10), 285 (11), 189.1 (100), 129 (96), 121 (97), 71 (79),
45 (32), 27 (8). Anal. Calcd for C20H22O2S: C, 73.59; H, 6.79.
Found: C, 73.55; H, 6.77.
Cu(MeCN)4PF6
6
7a
a
Product ratio was determined by 1H NMR (400 MHz) of the
crude product.
Exp er im en ta l Section
Gen er a l Meth od s. All reactions were performed under a
nitrogen atmosphere in a flame-dried reaction flask, and the
components were added via syringe. All solvents were distilled
prior to use. CH2Cl2, THF, and benzene were freshly distilled
from CaH2 before use. For the preparation of aryldiazoacetates,
see ref 17 and the references therein.
Typ ica l P r oced u r e for th e Rea ction of Ar yld ia zoa c-
eta te w ith Su lfid e Ca ta lyzed by Cu (I) Com p lex. In a
nitrogen atmosphere, Cu(MeCN)4PF6 (7.5 × 10-3 mmol, 2.7
mg) and ligand 7a (7.9 × 10-3 mmol, 2.3 mg) were added to a
25 mL round-bottom flask. Dry benzene (4.0 mL) was intro-
duced, and the solution was stirred for 1 h. To the slightly
blue solution was then added aryl sulfide 2 (Ar′ ) 2-CH3C6H4,
0.375 mmol, 61.5 mg) in benzene (2 mL). Methyl (p-methox-
yphenyl)diazoacetate (1, Ar ) p-MeOC6H4) (0.375 mmol, 77
mg) in dry benzene (6 mL) was added via a syringe over 30
min. The solution was stirred for additional 22 h. Solvent was
removed by evaporation, and the green oily residue was
purified by column chromatography (60:1 petroleum ether/
ethyl acetate) to give a colorless solid of 3 (Ar ) p-MeOC6H4,
Ar′ ) 2-CH3C6H4) (110 mg, 86%).
Meth yl 2-(1-n a p h th yl)-2-((2-m eth ylp h en yl)th io)-4-p en -
ten oa te (3, Ar ) 1-n a p h th yl, Ar ′ ) 2-CH3C6H4): HPLC (254
nm), 95:5 hexane/2-propanol, tR ) 26.819 min, tR ) 34.157 min;
1
mp 100-101 °C; IR (KBr) 3050 (m), 1722 (s); H NMR (200
MHz, CDCl3) δ 1.99 (s, 3H), 2.94-3.05 (s, 3H), 5.04-5.14 (m,
2H), 6.06-6.26 (m, 1H), 6.87-8.18 (m, 13H); 13C NMR (50
MHz, CDCl3) δ 20.63, 41.59, 52.43, 64.22, 118.44, 124.166,
124.22, 125.28, 125.38, 126.00, 128.97, 129.16, 129.25, 129.89,
130.16, 131.16, 133.28, 134.10, 135.16, 138.47, 144.51, 173.36;
MS (m/z, relative intensity) 362 (M+, 14), 321 (15), 303 (3),
261 (4), 239 (77), 211 (7), 207 (31), 179 (100), 165 (45), 152
(28), 127 (10), 115 (5), 91 (13), 71 (20), 59 (13), 45 (25), 27 (3).
Anal. Calcd for C23H22O2S: C, 76.21; H, 6.12. Found: C, 75.92;
H, 6.45.
Meth yl 2-(p-m eth oxylph en yl)-2-((2-m eth ylph en yl)th io)-
4-p en ten oa te (3, Ar ) p-MeOC6H4, Ar ′ ) 2-CH3C6H4):
HPLC (254 nm), 90:10 hexane/2-propanol, tR ) 27.518 min, tR
) 31.9 min; mp 76-78 °C; IR (KBr) 3084 (m), 1728 (s); 1H
NMR (200 MHz,CDCl3) δ 2.21 (s, 3H), 2.87-2.91 (m, 2H), 3.68
(s, 3H), 3.80 (s, 3H), 5.00-5.09 (m, 2H), 5.80-5.89 (m, 1H),
6.77-7.26 (m, 8H); 13C NMR (50 MHz, CDCl3) δ 20.73, 41.43,
52.29, 55.12, 63.95, 113.26, 118.44, 125.69, 128.72, 129.01,
130.25, 130.56, 131.65, 133.37, 137.32, 158.72, 172.37; MS
(m/z, relative intensity) 342 (M+, 4), 301 (5), 283 (2), 219.2
(100), 191 (5), 187 (5), 159 (64), 151 (50), 129 (9.5), 115 (12),
91 (11.5), 71 (16), 59 (58.5), 45 (16.5), 27 (12). Anal. Calcd for
Meth yl 2-ph en yl-2-((2-ch lor oph en yl)th io)-1-pen ten oate
(3, Ar ) C6H5, Ar ′ ) 2-ClC6H4): HPLC (254 nm), 90:10
hexane/2-propanol, tR ) 20.086 min, tR ) 22.626 min; mp 49-
51 °C; IR (KBr) 3072 (m), 1730 (s); 1H NMR (200 MHz, CDCl3)
δ 2.92-2.96 (m, 2H), 3.72 (s, 3H), 4.95-5.08 (m, 2H), 5.92-
6.01 (m, 1H), 7.05-7.36 (m, 9H); 13CNMR (50 MHz, CDCl3) δ
41.48, 52.48, 64.90, 118.69, 126.32, 127.45, 127.52, 127.89,
129.67, 129.97, 130.30, 132.97, 137.86, 138.84, 139.80, 171.67;
MS (m/z, relative intensity) 332 (M+, 8), 291 (9), 273 (5), 231
(4), 189 (70), 157 (25), 143 (10), 129.1 (100), 121 (52), 103 (10),
71 (50), 59 (18), 41 (8), 27 (3). Anal. Calcd for C18H17O2SCl:
C, 64.96; H, 5.15. Found: C, 64.98; H, 5.19.
Meth yl 2-p h en yl-2-(p h en ylth io)-1-p en ten oa te (3, Ar )
C6H5, Ar ′ ) C6H5): HPLC (254 nm), 85:15 hexane/2-propanol,
tR ) 19.453 min, tR ) 24.723 min; mp 72-73 °C; IR (KBr) 3063
(m), 1728 (s); 1H NMR (200 MHz, CDCl3) δ 2.84-2.89 (m, 2H),
3.69 (s, 3H), 5.02-5.14 (m, 2H), 5.91-6.01 (m, 1H), 7.16-7.31
C
20H22O3S: C, 70.15; H, 6.48. Found: C, 70.14; H, 6.51.
Meth yl 2-(m -m eth ylp h en yl)-2-((2-m eth ylp h en yl)th io)-
4-p en ten oa te (3, Ar ) m -MeC6H4, Ar ′ ) 2-CH3C6H4): HPLC
(254 nm), 99:1 hexane/2-propanol, tR ) 19.808 min, tR ) 25.019
min; mp 82-83 °C; IR (KBr) 3058 (m), 1725 (s); 1H NMR (200
MHz, CDCl3) δ 2.16 (s, 3H), 2.27 (s, 3H), 2.89-2.94 (m, 2H),
3.68 (s, 3H), 5.00-5.09 (m, 2H), 5.91-6.0 (m, 1H), 7.00-7.25
(m, 8H); 13C NMR (50 MHz, CDCl3) δ 20.73, 21.44, 30.82, 41.23,
52.42, 64.63, 118.52, 124.40, 125.72, 127.85, 128.12, 129.14,
130.275, 130.43, 133.38, 137.53, 137.59, 139.57, 144.05, 172.45;
MS (m/z, relative intensity) 326 (M+, 15), 285 (3), 267 (4), 225
(5), 203 (71), 175 (5), 171 (30), 143 (100), 135 (66), 115 (15), 91
5624 J . Org. Chem., Vol. 67, No. 16, 2002