Pauson ± Khand Reactions
2435±2448
endo-9 f : 1H NMR (300 MHz, CDCl3): d 8.03 ± 7.95 (m, 2H, ArH), 7.77 ±
7.52 (m, 3H, ArH), 5.88 (m, 1H, H2), 4.22 (d, J 2.9 Hz, 1H, H6), 3.80 (t,
J 2.7 Hz, 1H, H4), 3.55 (m, 1H, H5), 3.25 (s, 3H, OMe), 2.63 (m, 2H, H8),
2.28 (m, 1H, H7), 2.13 (m, 1H, H7); 13C NMR (50 MHz, CDCl3): d 198.1,
186.6, 138.5, 133.9, 129.1, 129.0, 124.8, 77.8, 67.9, 56.4, 53.2, 30.4, 24.3.
endo-13b: 1H NMR (300 MHz, CDCl3): d 8.01 ± 7.95 (m, 2H, ArH),
7.71 ± 7.55 (m, 3H, ArH), 5.85 (m, 1H, H2), 4.72/4.63 (AB system, J
6.6 Hz, 2H, OCH2O), 4.24 (d, J 4.2 Hz, 1H, H6), 3.93 (m, 1H, H5), 3.71
(d, J 4.5 Hz, 1H, H4), 3.56 (q, J 6.9 Hz, 2H, OCH2CH3), 2.49 (m, 2H,
H8), 1.24 (s, 3H, CH3), 1.19 (t, J 6.9 Hz, 3H, OCH2CH3), 1.15 (s, 3H,
CH3); 13C NMR (75 MHz, CDCl3): d 197.7, 186.2, 138.7, 133.9, 129.2,
125.2, 96.8, 85.4, 69.1, 64.4, 51.7, 46.4, 40.3, 29.4, 24.3, 15.0.
exo-13b: 1H NMR (300 MHz, CDCl3): d 8.05 ± 7.99 (m, 2H, ArH), 7.71 ±
7.57 (m, 3H, ArH), 5.88 (m, 1H, H2), 4.96/4.69 (AB system, J 7.6 Hz, 2H,
OCH2O), 3.96 (d, J 3.1 Hz, 1H, H6), 3.79 (m, 1H, H5), 3.68 (m, 1H,
OCH2CH3), 3.47 (d, J 9.7 Hz, 1H, H4), 2.67/2.45 (AB system, J 18.2 Hz,
2H, H8), 1.26 (s, 3H, CH3), 1.25 (t, J 6.9 Hz, 3H, OCH2CH3), 1.12 (s, 3H,
CH3); 13C NMR (75 MHz, CDCl3): d 196.9, 182.6, 139.2, 134.0, 129.3,
126.2, 94.3, 85.2, 63.6, 51.2, 41.8, 28.8, 24.7, 15.0.
exo-9 f: 1H NMR (300 MHz, CDCl3): d 7.99 ± 7.91 (m, 2H, ArH), 7.77 ±
7.55 (m, 3H, ArH), 5.90 (m, 1H, H2), 3.92 (d, J 2.8 Hz, 1H, H6), 3.50 (m,
2H, H4, H5), 3.38 (s, 3H, OMe), 2.83 (m, 1H, H8), 2.60 (m, 1H, H8), 2.36
(m, 1H, H7), 2.14 (m, 1H, H7); 13C NMR (75 MHz, CDCl3): d 197.0,
185.1, 138.1, 134.0, 129.3, 128.8, 125.8, 83.0, 72.1, 57.5, 52.7, 31.3, 25.0.
6-Ethoxymethoxy-2-methyl-4-(phenylsulfonyl)bicyclo[3.3.0]oct-1-en-3-
one (11b): When method B was used, treatment of 3b (69 mg, 0.21 mmol)
with [Co2(CO)8] (81 mg, 0.24 mmol) and Me3NO ´ 2H2O (162 mg,
1.47 mmol) afforded, after chromatographic purification (hexane/ethyl
acetate 5:1), endo-11b (54 mg, 71%, colourless oil) and exo-11b (3 mg,
5%, colourless oil).
7,7-Dimethyl-4-phenylsulfonyl-6-(triisopropylsiloxy)bicyclo[3.3.0]oct-1-
en-3-one (13c): When method B was used, treatment of 5c (48 mg,
0.11 mmol) with [Co2(CO)8] (51 mg, 0.15 mmol) and Me3NO ´ 2H2O
(85 mg, 0.77 mmol) afforded, after chromatographic purification (hexane/
ethyl acetate 10:1), endo-13c (15 mg, 25%, colourless oil) and exo-13c
(22 mg, 43%, colourless oil).
endo-13c: 1H NMR (200 MHz, CDCl3): d 8.00 ± 7.94 (m, 2H, ArH), 7.78 ±
7.54 (m, 3H, ArH), 5.85 (m, 1H, H2), 4.25 (m, 1H, H6), 3.99 (m, 2H, H4,
H5), 2.48 (m, 2H, H8), 1.08 (m, 27H, C(CH3)2, TIPS); 13C NMR (75 MHz,
CDCl3): d 197.2, 184.5, 138.1, 134.0, 129.3, 126.0, 82.2, 71.3, 52.9, 44.2, 41.8,
28.7, 24.5, 18.3, 13.5; MS (70 eV, EI): m/z (%): 419 (100), 321 (6), 277 (4),
219 (2), 149 (15), 121, (12), 77 (22), 57 (34).
endo-11b: 1H NMR (300 MHz, CDCl3): d 8.00 ± 7.94 (m, 2H, ArH), 7.75
(m, 3H, ArH), 4.70/4.61 (AB system, J 6.9 Hz, 2H, OCH2O), 4.31 (m,
1H, H6), 4.19 (d, J 4.0 Hz, 1H, H4), 3.52 (m, 3H, H5, OCH2CH3), 2.48
(m, 2H, H8), 2.26 (m, 2H, H7), 1.68 (s, 3H, CH3), 1.24 (t, J 7.0 Hz, 3H,
OCH2CH3); 13C NMR (50 MHz, CDCl3): d 198.3, 179.2, 138.7, 133.9,
132.9, 132.7, 129.1, 128.9, 93.7, 74.5, 67.7, 63.6, 50.8, 32.3, 23.2, 15.0.
exo-11b: 1H NMR (300 MHz, CDCl3): d 8.02 ± 7.94 (m, 2H, ArH), 7.75
(m, 3H, ArH), 4.80/4.66 (AB system, J 7.2 Hz, 2H, OCH2O), 3.86 (d, J
3.0 Hz, 1H, H4), 3.79 (m, 1H, H6), 3.50 (m, 3H, H5, OCH2CH3), 2.70 (m,
1H, H5), 2.55 (m, 1H, H8), 2.33 (m, 1H, H8), 2.26 (m, 1H, H7), 1.55 (s, 3H,
CH3), 1.21 (t, J 7.0 Hz, 3H, OCH2CH3); HRMS (FAB ): calcd for:
1
exo-13c: H NMR (200 MHz, CDCl3): d 7.97 ± 7.81 (m, 2H, ArH), 7.76 ±
7.55 (m, 3H, ArH), 5.89 (m, 1H, H2), 3.86 (m, 1H, H6), 3.67 (d, J 7.9 Hz,
1H, H4), 3.55 (m, 1H, H5), 2.43 (m, 2H, H8), 1.13 (s, 27H, C(CH3)2, TIPS);
13C NMR (75 MHz, CDCl3): d 198.1, 184.5, 138.7, 134.5, 129.2, 128.9,
124.9, 80.0, 68.7, 52.6, 47.1, 40.0, 29.3, 24.8, 18.3, 13.8; HRMS (FAB ):
351.1266; found: 351.1254 [MH] .
2-Methyl-4-phenylsulfonyl-6-(triisopropylsiloxy)bicyclo[3.3.0]oct-1-en-3-
one (11c): When method B was used, treatment of 3c (59 mg, 0.14 mmol)
with [Co2(CO)8] (55 mg, 0.16 mmol) and Me3NO ´ 2H2O (108 mg,
0.98 mmol) afforded, after chromatographic purification (hexane/ethyl
acetate 10:1), endo-11c (39 mg, 63%, colourless oil) and exo-11c (4 mg,
7%, colourless oil).
calcd for: 463.2338; found: 463.2328 [MH] .
7,7-Dimethyl-6-hydroxy-2-phenyl-4-(phenylsulfonyl)bicyclo[3.3.0]oct-1-
en-3-one (15a): When method C was used, treatment of 7a (88 mg,
0.25 mmol) with [Co2(CO)8] (92 mg, 0.27 mmol), Me3NO ´ 2H2O (194 mg,
1.75 mmol) and molecular sieves (4 , 704 mg) afforded, after chromato-
graphic purification (hexane/ethyl acetate 1:1), endo-15a and exo-15a
(71 mg, 75%) as an inseparable endo/exo mixture (76/24). 1H NMR
(300 MHz, CDCl3): d 8.19 ± 7.95 (m, 4H, ArH, endoexo), 7.87 ± 7.21 (m,
6H, ArH, endoexo), 4.44 (d, J 3.5 Hz, 1H, H6 endo), 4.08 (m, 1H, H6
exo), 3.92 (m, 1H, H4 endo), 3.91 (m, 1H, H5 endo), 3.86 (m, 1H, H4 endo),
3.77 (m, 1H, H8 exo), 3.59 (m, 1H, H8 endo), 3.40 (m, 1H, H5 exo), 2.90 (m,
2H, H8 exo), 1.70 (m, 2H endo), 1.34 ± 1.15 (m, endoexo); 13C NMR
(75 MHz, CDCl3): d 196.3, 194.9, 180.3, 176.8, 138.5, 136.1, 135.5, 132.0,
134.9, 134.3, 133.9, 130.4, 129.5, 129.0, 128.9, 128.6, 128.4, 128.2, 128.1, 127.2,
81.9, 76.7, 74.4, 68.9, 50.9, 50.1, 46.0, 44.3, 43.4, 41.1, 28.9, 28.0, 23.5, 23.4;
endo-11c: 1H NMR (300 MHz, CDCl3): d 7.98 ± 7.95 (m, 2H, ArH), 7.69 ±
7.55 (m, 3H, ArH), 4.61 (m, 1H, H6), 4.05 (d, J 4.2 Hz, 1H, H4), 3.50 (m,
1H, H5), 2.50 (m, 2H, H8), 2.21 (m, 2H, H7), 1.69 (s, 3H, CH3), 0.99 (s,
21H, TIPS); 13C NMR (50 MHz, CDCl3): d 198.7, 180.2, 138.8, 133.8,
132.9, 129.2, 128.8, 70.8, 67.8, 52.2, 35.9, 23.1, 17.9, 12.3; MS (70 eV, EI): m/z
(%): 405 (100), 265 (2), 255 (2), 191 (3), 125 (8), 91 (4), 77 (9); HRMS
(FAB ): calcd for: 449.2181; found: 449.2182 [MH] .
1
exo-11c: H NMR (300 MHz, CDCl3): d 7.99 ± 7.94 (m, 2H, ArH), 7.67 ±
7.54 (m, 3H, ArH), 4.61 (m, 1H, H6), 4.11 (m, 1H, H4), 3.55 (m, 1H, H5),
2.64 (m, 2H, H8), 2.22 (m, 2H, H7), 1.66 (s, 3H, CH3), 1.01 (s, 21H, TIPS);
13C NMR (50 MHz, CDCl3): d 199.0, 180.2, 138.5, 133.9, 131.9, 129.2,
128.9, 70.9, 67.9, 52.3, 35.7, 23.2, 18.0, 12.3; MS (70 eV, EI): m/z (%): 405
(100), 391 (48), 265 (3), 255 (3), 191 (4), 91 (6), 77 (14); HRMS (FAB ):
HRMS (FAB ): calcd for: 383.1317; found: 383.1305 [MH] .
7,7-Dimethyl-6-ethoxymethoxy-2-phenyl-4-(phenylsulfonyl)bicy-
clo[3.3.0]oct-1-en-3-one (15b): When method C was used, treatment of 7b
(30 mg, 0.07 mmol) with [Co2(CO)8] (27 mg, 0.08 mmol), Me3NO ´ 2H2O
(54 mg, 0.49 mmol) and molecular sieves (4 , 240 mg) afforded, after
chromatographic purification (hexane/ethyl acetate 4:1), endo-15b and
exo-15b (25 mg, 79%) as an inseparable endo/exo mixture (87:13). 1H NMR
(300 MHz, CDCl3): d 8.09 ± 8.00 (m, 3H, ArH endoexo), 7.77 ± 7.55 (m,
3H, ArH endoexo), 7.44 ± 7.16 (m, 5H, ArH endoexo), 4.77 (m, 4H,
OCH2O endoexo), 4.45 (d, J 4.1 Hz, 1H, H6 endo), 4.15 (m, 1H, H6
exo), 4.05 (m, 1H, H5 endo), 3.83 (d, J 4.2 Hz, 1H, H4 endo), 3.70 (d, J
4.0 Hz, 1H, H4 exo), 3.66 (m, 5H, OCH2CH3 endoexo, H5 exo), 2.85/2.83
(AB system, J 16.0 Hz, 2H, H8 endo), 2.70 (m, 2H, H8 exo), 1.35 ± 1.10
(m, 18H, endoexo); 13C NMR (75 MHz, CDCl3): d 196.3, 195.3, 180.0,
177.1, 138.8, 134.9, 134.0, 130.1, 129.3, 128.9, 128.3, 128.1, 96.8, 95.1, 85.1,
84.5, 70.3, 69.6, 64.5, 63.2, 49.6, 48.0, 46.5, 41.7, 37.5, 29.7, 29.5, 24.4, 15.0;
calcd for: 449.2181; found: 449.2175 [MH] .
7,7-Dimethyl-6-hydroxy-4-(phenylsulfonyl)bicyclo[3.3.0]oct-1-en-3-one
(13a): When method C was used, treatment of 5a (50 mg, 0.18 mmol) with
[Co2(CO)8] (68 mg, 0.20 mmol), Me3NO ´ 2H2O (140 mg, 1.26 mmol) and
4 molecular sieves (400 mg) afforded endo-13a and exo-13a (33 mg,
60%) as an inseparable endo/exo mixture (80/20). 1H NMR (200 MHz,
C6D6): d 8.23 (m, 2H, ArH), 8.17 (m, 2H, ArH), 7.00 (m, 6H, ArH), 5.56
(m, 1H, H2 endo), 5.44 (m, 1H, H2 exo), 4.38 (d, J 4.5 Hz, 1H, H6 endo),
4.04 (m, 1H, H5 endo), 3.66 (m, 1H, H6 exo), 3.51 (m, 1H, H4 endo), 3.46
(d, J 5.0 Hz, 1H, H5 exo), 3.10 (m, 1H, H4 exo), 1.75 (m, 4H, H8
endoexo), 0.90 (s, 3H, CH3), 0.85 (s, 3H, CH3), 0.71 (s, 3H, CH3), 0.69 (s,
3H, CH3); 13C NMR (50 MHz, CDCl3): d 197.8, 196.5, 186.6, 182.1, 138.5,
137.6, 134.4, 134.0, 129.5, 129.2, 129.0, 125.8, 125.2, 82.0, 77.1, 73.9, 78.5, 53.0,
52.2, 46.1, 43.5, 41.7, 39.8, 29.6, 28.1, 23.6, 23.3; HRMS (FAB ): calcd for:
HRMS (FAB ): calcd for: 441.1735; found: 441.1747 [MH] .
307.1004; found: 307.1014 [MH] .
7,7-Dimethyl-2-phenyl-4-phenylsulfonyl-6-(triisopropylsiloxy)bicy-
7,7-Dimethyl-6-ethoxymethoxy-4-(phenylsulfonyl)bicyclo[3.3.0]oct-1-en-
3-one (13b): When method B was used, treatment of 5b (67 mg,
0.20 mmol) with [Co2(CO)8] (75 mg, 0.22 mmol) and Me3NO ´ 2H2O
(155 mg, 1.40 mmol) afforded, after chromatographic purification (hex-
ane/ethyl acetate 6:1), endo-13b (34 mg, 47%, colourless oil) and exo-13b
(18 mg, 25%, colourless oil).
clo[3.3.0]oct-1-en-3-one (15c): When method C was used, treatment of 7c
(63 mg, 0.12 mmol) with [Co2(CO)8] (46 mg, 0.13 mmol), Me3NO ´ 2H2O
(93 mg, 0.84 mmol) and molecular sieves (4 , 504 mg) afforded, after
chromatographic purification (hexane/ethyl acetate 8:1), endo-15c and
exo-15c (51 mg, 78%) as an inseparable endo/exo mixture (94/6). 1H NMR
(300 MHz, CDCl3): d 8.04 ± 8.00 (m, 4H, ArH endoexo), 7.87 ± 7.55 (m,
Chem. Eur. J. 2001, 7, No. 11
ꢀ WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2001
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