6552
M. Zaja et al. / Tetrahedron 59 (2003) 6545–6558
2919, 1482, 1419, 1257, 1213, 1133, 929 cm21; MS (70 eV,
EI): m/z (%): 644 (17), 442 (12), 406 (18), 327 (12), 304
(100), 301 (18), 248 (28), 236 (34), 155 (19), 138 (50), 127
(57), 91 (69), 69 (46), 57 (96); HR-MS: calcd: 644.1304;
found: 644.1316; elemental analysis calcd (%) for C31H37-
N2OFCl2Ru (644.61): C 57.76, H 5.79, N 4.35; found: C
58.06, H 6.12, N 4.08.
(15), 272 (29), 256 (10), 177 (10), 152 (27), 123 (21), 111
(28), 97 (44), 83 (62), 55 (100); HR-MS: calcd: 656.1504;
found: 656.1519; elemental analysis calcd (%) for C32H40-
O2N2Cl2Ru (656.66): C 58.53, H 6.14, N 4.27; found: C
58.18, H 5.90, N 4.51.
4.2.5. (4,5-DihydroIMes)Cl2RuvCH(2-OiPr)(4-F)C6H3
(12). The procedure for the synthesis of catalyst 10 was
followed using 3 (100 mg, 0.118 mmol), 20 (21.2 mg,
0.118 mmol) and CuCl (11.7 mg, 0.118 mmol) in CH2Cl2
(2.4 mL). FC (hexane/EtOAc 7:1) gave 12 as a green solid
4.2.2. (4,5-DihydroIMes)Cl2RuvCH(2-OiPr)(5-
Me)C6H3 (8). The procedure for the synthesis of catalyst
10 was followed using 3 (200 mg, 0.235 mmol), 16 (83 mg,
0.471 mmol) and CuCl (23.3 mg, 0.235 mmol) in CH2Cl2
(30 mL). FC (CH2Cl2/hexane 1:1) gave 8 as a green solid
1
(48 mg, 63%). H NMR (400 MHz, CDCl3): d¼16.59 (s,
1H), 7.40 (d, J¼8 Hz, 1H), 6.98 (s, 4H), 6.38 (td, J¼8,
2.2 Hz, 1H), 6.21 (d, J¼10.3 Hz, 1H), 4.23 (septet,
J¼6.0 Hz, 1H), 3.44 (s, 4H), 2.60 (bs, 12H), 2.26 (s, 6H),
1.25 (d, J¼6.0 Hz, 6H) ppm; IR (Nujol): n¼3503, 2966,
2917, 2859, 1712, 1592, 1484, 1429, 1270, 1255, 1155,
1101, 990, 839 cm21; MS (70 eV, EI): m/z (%): 644 (14),
442 (12), 406 (20), 304 (100), 301 (20), 158 (20), 138 (18),
111 (22), 91 (49), 71 (52), 57 (83); HR-MS: calcd:
644.1304; found: 644.1315.
1
(123 mg, 82%). H NMR (500 MHz, CDCl3): d¼16.50 (s,
1H), 7.28 (d, J¼8.4 Hz, 1H), 7.07 (s, 4H), 6.69 (s, 1H), 6.66
(d, J¼8.4 Hz, 1H), 4.84 (septet, J¼6.0 Hz, 1H), 4.17 (s,
4H), 2.48 (bs, 12H), 2.41 (s, 6H), 2.34 (s, 3H), 1.25 (d,
J¼6.0 Hz, 6H) ppm; 13C NMR (125 MHz, CD2Cl2):
d¼297.8, 211.8, 150.4, 145.4, 138.9, 131.5, 130.0, 129.5,
123.1, 112.6, 74.8, 51.6, 21.1, 20.1 ppm; IR (Nujol):
n¼2974, 2918, 2857, 1701, 1486, 1419, 1260, 1221, 1135,
1104, 925, 853 cm21; MS (70 eV, EI): m/z (%): 640 (26),
526 (12), 507 (12), 478 (30), 442 (13), 406 (31), 395 (60),
377 (52), 341 (20), 307 (21), 304 (76), 287 (19), 250 (14),
210 (13), 171 (39), 147 (28), 134 (37), 121 (24), 91 (31), 73
(100), 57 (48); HR-MS: calcd: 640.1555; found: 640.1552;
elemental analysis calcd (%) for C32H40N2OCl2Ru
(640.66): C 59.99, H 6.29, N 4.37; found: C 59.96, H
6.49, N 4.32.
4.2.6. (4,5-DihydroIMes)Cl2RuvCH(2,5-OiPr)C6H3 (7).
The procedure for the synthesis of catalyst 10 was followed
using 3 (189 mg, 0.222 mmol), 15 (48.4 mg, 0.222 mmol)
and CuCl (21.8 mg, 0.222 mmol) in CH2Cl2 (4.0 mL). FC
(CH2Cl2/hexane 1:1) gave 7 as a green solid (48 mg, 63%).
1H NMR (500 MHz, C6D6): d¼16.61 (s, 1H), 7.20–6.90
(m, 5H), 6.76 (d, J¼3.0 Hz, 1H), 6.29 (d, J¼9.0 Hz, 1H),
4.50 (septet, J¼6.0 Hz, 1H), 4.19 (septet, J¼6.0 Hz, 1H),
3.49 (s, 4H), 2.62 (bs, 12H), 2.28 (s, 6H), 1.38 (d, J¼6.0 Hz,
6H), 1.20 (d, J¼6.0 Hz, 6H) ppm; IR (Nujol): n¼3485,
2976, 2920, 1701, 1607, 1579, 1485, 1419, 1257, 1215,
1137, 1104, 942 cm21; MS (70 eV, EI): m/z (%): 684 (42),
570 (14), 527 (13), 442 (13), 405 (48), 304 (100), 301 (44),
287 (20), 136 (56), 124 (37), 97 (29), 81 (43), 69 (91); HR-
MS: calcd: 684.1817; found: 684.1819; elemental analysis
calcd (%) for C34H44N2Cl2O2Ru (684.72): C 59.64, H 6.48,
N 4.09; found: C 59.95, H 6.78, N 3.78.
4.2.3. (4,5-DihydroIMes)Cl2RuvCH(2,4-bis-OiPr)C6H3
(11). The procedure for the synthesis of catalyst 10 was
followed using 3 (200 mg, 0.235 mmol), 19 (104 mg,
0.472 mmol) and CuCl (23.3 mg, 0.235 mmol) in CH2Cl2
(30 mL). FC (CH2Cl2/hexane 1:1) gave 11 as a green solid
1
(135 mg, 81%). H NMR (500 MHz, CDCl3): d¼16.17 (s,
1H), 7.05 (s, 4H), 6.80 (d, J¼8.5 Hz, 1H), 6.37 (dd, J¼8.5,
1.8 Hz, 1H), 6.30 (s, 1H), 4.81 (septet, J¼6.1 Hz, 1H), 4.51
(septet, J¼6.1 Hz, 1H), 4.17 (s, 4H), 2.47 (bs, 12H), 2.39 (s,
6H), 1.28 (d, J¼6.1 Hz, 6H), 1.26 (d, J¼6.1 Hz, 6H) ppm;
IR (Nujol): n¼2976, 2923, 2854, 1596, 1482, 1437, 1384,
1264, 1254, 1116, 1100, 842 cm21; MS (70 eV, EI): m/z
(%): 684 (3), 510 (9), 412 (3), 312 (10), 304 (100), 289 (10),
250 (13), 215 (9), 171 (19), 136 (21), 91 (26), 57 (14); HR-
MS: calcd: 684.1817; found: 684.1821; elemental analysis
calcd (%) for C34H44N2Cl2O2Ru (684.72): C 59.64, H 6.48,
N 4.09; found: C 59.34, H 6.85, N 3.51.
4.2.7. (4,5-DihydroIMes)Cl2RuvCH(2-OiPr)(5-
CF3)C6H3 (9). The procedure for the synthesis of catalyst
10 was followed using 3 (200 mg, 0.236 mmol), 17
(54.3 mg, 0.236 mmol) and CuCl (23.3 mg, 0.236 mmol)
in CH2Cl2 (5.0 mL). FC (hexane/EtOAc 7:1) gave 9 as a
1
green solid (111 mg, 68%). H NMR (400 MHz, CDCl3):
d¼16.46 (s, 1H), 7.77 (dd, J¼9.0, 2.0 Hz, 1H), 7.18 (d,
J¼2.0 Hz, 1H), 7.04 (s, 4H), 6.97 (d, J¼9.0 Hz, 1H), 4.97
(septet, J¼6.0 Hz, 1H), 4.11 (s, 4H), 2.57 (s, 12H), 2.41 (s,
6H), 1.25 (d, J¼6.0 Hz, 6H) ppm; IR (Nujol): n¼3493,
2976, 2920, 2863, 1705, 1599, 1492, 1483, 1421, 1331,
4.2.4. (4,5-DihydroIMes)Cl2RuvCH(2-OiPr)(3-
OMe)C6H3 (14). The procedure for the synthesis of catalyst
10 was followed using 3 (300 mg, 0.353 mmol), 22
(136 mg, 0.707 mmol) and CuCl (38.4 mg, 0.388 mmol)
in CH2Cl2 (35 mL). FC (hexane/MTBE 2:1) gave 14 as a
1282, 1263, 1212, 1166, 1130, 1101, 1072, 910, 854 cm21
;
MS (70 eV, EI): m/z (%): 694 (30), 442 (28), 406 (40), 348
(100), 304 (78), 301 (35), 215 (28), 188 (46), 176 (37), 91
(28), 57 (20); HR-MS: calcd: 694.1272; found: 694.1269.
1
green solid (188 mg, 81%). H NMR (500 MHz, CD2Cl2):
d¼16.51 (s, 1H), 7.15 (d, J¼8.0 Hz, 1H), 7.09 (bs, 4H), 6.90
(dd, J¼8.0, 7.5 Hz, 1H), 6.58 (d, J¼7.5 Hz, 1H), 5.73
(septet, J¼6.2 Hz, 1H), 4.13 (s, 4H), 3.79 (s, 3H), 2.45 (bs,
18H), 1.20 (d, J¼6.2 Hz, 6H) ppm; 13C NMR (125 MHz,
CD2Cl2): d¼297.4, 210.7, 149.8, 147.7, 139.9, 139.7, 138.9,
138.8, 129.3, 123.6, 115.5, 114.2, 80.6, 56.4, 51.5, 21.6,
20.9, 20.2, 18.4 ppm; IR (Nujol): n¼3482, 1701, 1607,
1585, 1574, 1475, 1445, 1419, 1267, 1106 cm21; MS
(70 eV, EI): m/z (%): 656 (2), 578 (6), 404 (10), 356 (9), 304
4.2.8. (4,5-DihydroIMes)Cl2RuvCH(2-OiPr)(4-
CN)C6H3 (13). The procedure for the synthesis of catalyst
10 was followed using 3 (227 mg, 0.267 mmol), 21
(50.0 mg, 0.267 mmol) and CuCl (26.9 mg, 0.267 mmol)
in CH2Cl2 (5.3 mL). FC (CH2Cl2/hexane 3:1) gave 13 as a
1
green solid (36 mg, 21%). H NMR (400 MHz, CDCl3):
d¼16.63 (s, 1H), 7.21 (d, J¼9.0 Hz, 1H), 7.05 (s, 4H),