Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2001
Experimental Section
General:
Melting points were taken on a Büchi 530 apparatus and are uncorrected. 1H NMR and 13C
NMR spectra were recorded on a Brucker AM-300 instrument at 300 and 75.43 MHz
respectively. NMR spectra were registered in CDCl3 and chemical shifts are given in ppm
relative to TMS (1H, 0.00 ppm) or CDCl3 (13C, 77.00 ppm). IR spectra were recorded on a
Perkin-Elmer 1330 infrared spectrophotometer. For purification of crude reaction mixtures
flash chromatography was applied in all cases. Merck silica-gel (230-400 mesh) was used as
the stationary phase. TMANO (trimethylamine N-oxide) was dehydrated by refluxing
overnight a toluene solution using a Dean-Stark apparatous. 4Å Molecular sieves, (beads, 812 mesh, Aldrich) were powdered by vigorous stirring in toluene overnight. After filtration,
the powder was dried in an oven for 4 h at 120ºC.
General procedure for the Pauson-Khand reaction.
Method A: 1.00 mmol of the enyne 1 was dissolved in dry toluene (40 mL) at room
temperature under argon, in a flask containing eight times the mass of the enyne of powdered
4Å molecular sieves. To this solution, 1.20 mmol of Co2(CO)8 were added and the resulting
mixture was stirred for 2 h until total complexation of the enyne (t.l.c.). The reaction was then
cooled to -10ºC with an ice/salt bath, and a suspension of Me3NO (9.00 mmol) in toluene at
0ºC was added dropwise. After 18 h of stirring, the mixture was filtrated, the solvent was
evaporated under vacuum and the crude was purified and/or separated by flash
chromatography (hexane/EtOAc mixtures).
Method B: 1.00 mmol of the enyne 1 was dissolved in dry toluene (40 mL) at room
temperature under argon, in a flask containing eight times the mass of the enyne of powdered
4Å molecular sieves. To this solution, 1.20 mmol of Co2(CO)8 were added and the resulting
mixture was stirred for 2 h until total complexation of the enyne (t.l.c.). The reaction was
refluxed for 18 h. After filtration and solvent elimination the crude was purified and/or
separated by flash chromatography (hexane/EtOAc mixtures).
Method C: 1.00 mmol of the enyne 1 was dissolved in dry toluene (40 mL) at room
temperature under argon. To this solution, 1.20 mmol of Co2(CO)8 were added and the
resulting mixture was stirred for 2 h until total complexation of the enyne (t.l.c.). The reaction
was refluxed for 18 h. After filtration and solvent elimination the crude was purified and/or
separated by flash chromatography (hexane/EtOAc mixtures).
Preparation of 5. Following Method A, from 0.2 g (0.89 mmol) of 1, 0.36 g (1.07 mmol) of
Co2(CO)8, 1.6 g of molecular sieves and 0.60 g (8.01 mmol) of TMANO, 0.04 g (20%) of 5
was obtained as a pale yellow oil, and following Method B, from 0.25 g (1.11 mmol) of 1,
0.46 g (1.33 mmol) of Co2(CO)8 and 2.0 g of molecular sieves, 0.02 g (10%) of 5 was
obtained.
1
H NMR CDCl3  1.60 (t, 1H, J= 13.7. Hz), 2.08 (dd, 1H, J 1= 19.2 Hz, J2= 2.2 Hz), 2.652.74 (m, 1H), 2.77 (dd, 1H, J1= 19.2 Hz, J2= 6.6 Hz), 3.64-3.72 (m, 1H), 5.02 (d, 1H, J= 13.7
Hz), 5.26-5.30 (m, 2H), 6.11(s, 1H), 6.43 (s, 1H); 7.11 (t, 1H, J= 7.7 Hz), 7.27 (t, 1H, J= 8.2
Hz), 7.38 (d, 1H, J= 8.8 Hz), 7.57 (d, 1H, J= 7.7 Hz) 13C NMR  CDCl3 208.0, 174.6,
141.0, 136.9, 132.0, 127.0, 122.5, 121.0, 119.9, 108.6, 101.9, 66.4, 44.4, 42.9, 39.7, 38.3; IR
(neat)  3250, 2940, 1720 cm-1.
Preparation of 6. Following Method A, from 0.2 g (0.59 mmol) of 2, 0.24 g (0.71 mmol) of
Co2(CO)8, 1.6 g of molecular sieves and 0.40 g (5.31 mmol) of TMANO, 0.14 g (65%) of 6
was obtained as a pale yellow oil, following Method B, from 0.2 g (0.59 mmol) of 2, 0.24 g
(0.71 mmol) of Co2(CO)8 and 1.6 g of molecular sieves, 0.16 g (75%) of 6 was obtained and,
following Method C, from 0.2 g (0.59 mmol) of 2 and 0.24 g (0.71 mmol) of Co2(CO)8, 0.09
g (40%) of 6 was obtained.
Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2001
H NMR CDCl3  -0.13 (s, 3H), 0.15 (s, 3H), 0.90 (s, 9H), 1.56 (dd, 1H, J1= 13.2. Hz, J2=
12.6 Hz), 2.08 (dd, 1H, J1= 19.2 Hz, J2= 2.2 Hz), 2.55-2.63 (m, 1H), 2.77 (dd, 1H, J1= 19.2
Hz, J2= 6.6 Hz), 3.62-3.71 (m, 1H), 4.98 (d, 1H, J= 13.5 Hz), 5.21 (d, 1H, J= 6.0 Hz); 5.27 (d,
1H, J= 13.5 Hz), 6.10 (s, 1H), 6.36 (s, 1H), 7.10 (t, 1H, J= 7.7 Hz), 7.25 (t, 1H, J= 8.2 Hz),
7.38 (d, 1H, J= 8.2 Hz), 7.57 (d, 1H, J= 7.7 Hz) 13C NMR  CDCl3 207.8, 174.6, 141.2,
136.6, 131.9, 127.1, 121.9, 120.9, 119.5, 108.5, 101.0, 66.9, 44.2, 42.8, 41.4, 38.4, 25.7, 18.0,
-5.1, -5.4; IR (neat)  2920, 1710, 1460 cm-1.
Preparation of 7. Following Method A, from 0.3 g (0.85 mmol) of 3, 0.35 g (1.02 mmol) of
Co2(CO)8, 2.4 g of molecular sieves and 0.57 g (7.65 mmol) of TMANO, 0.03 g (10%) of 7
was obtained as a pale yellow solid (mp>180º dec.), and following Method B, from 0.3 g
(0.85 mmol) of 3, 0.35 g (1.02 mmol) of Co2(CO)8 and 2.4 g of molecular sieves, 0.09 g
(30%) of 7 was obtained.
1
H NMR CDCl3  2.17 (dd, 1H, J1= 18.7. Hz, J2= 2.2 Hz), 2.49-2.57 (m, 1H) 2.70-2.85 (m,
2H), 3.21-3.29 (m, 1H), 4.83 (d, 1H, J= 15.4 Hz), 5.52 (d, 1H, J= 14.8 Hz), 5.84 (d, 1H, J=
11.0 Hz), 6.11 (d, 1H, J= 3.3 Hz), 7.07 (t, 1H, J= 7.7 Hz), 7.22 (t, 1H, J= 7.7 Hz), 7.38 (d, 1H,
J= 8.2 Hz), 7.45 (d, 1H, J= 7.7 Hz), 7.78-7.81 (m, 2H), 7.92-7.94 (m, 2H) 13C NMR 
CDCl3 206.9, 172.5, 167.5, 138.0, 136.8, 134.4, 132.1, 131.6, 127.1, 123.7, 122.0, 120.7,
120.0, 108.5, 100.3, 48.2, 44.2, 42.8, 38.4, 29.6. IR (KBr)  1780, 1710, cm-1.
Preparation of 8. Following Method A, from 0.2 g (0.49 mmol) of 4, 0.2 g (0.58 mmol) of
Co2(CO)8, 1.6 g of molecular sieves and 0.33 g (4.41 mmol) of TMANO, 0.03 g (15%) of 8
was obtained as a yellow oil, following Method B, from 0.2 g (0.49 mmol) of 4, 0.2 g (0.58
mmol) of Co2(CO)8, 1.6 g of molecular sieves, 0.08 g (40%) of 8 was obtained, and following
Method C, 0.2 g (0.49 mmol) of 4, 0.2 g (0.58 mmol) of Co2(CO)8, 0.02 g (10%) of 8 was
obtained.
1
H NMR CDCl3  0.07 (s, 3H), 0.16 (s, 3H), 0.27 (s, 9H), 0.97 (s, 9H), 2.14 (dd, 1H, J1=
18.1. Hz, J2= 3.3 Hz), 2.73 (dd, 1H, J1= 18.6. Hz, J2= 7.5 Hz), 2.86 (dd, 1H, J1= 14.4. Hz, J2=
9.3 Hz) 3.15-3.17 (m, 1H), 3.45 (dd, 1H, J1= 14.4. Hz, J2= 2.1 Hz), 3.77 (dd, 1H, J1= 14.4.
Hz, J2= 10.5 Hz), 4.59 (dd, 1H, J1= 13.5. Hz, J2= 3.3 Hz), 5.04 (dd, 1H, J1= 9.0. Hz, J2= 2.1
Hz), 6.50 (s, 1H), 7.11 (t, 1H, J= 7.2 Hz), 7.19 (t, 1H, J= 7.4 Hz), 7.32 (d, 1H, J= 8.1 Hz),
7.61 (d, 1H, J= 7.8 Hz) 13C NMR  CDCl3 211.1, 184.1, 143.4, 142.5, 137.0, 127.3, 121.4,
120.7, 119.7, 108.6, 99.9, 67.1, 46.8, 44.9, 42.9, 40.6, 25.7, 18.2, -0.2, -4.5, -5.1. IR (neat) 
2960, 2860, 1690, cm-1.
Preparation of 10. Following Method A, from 0.25 g (0.86 mmol) of 9, 0.35 g (1.04 mmol)
of Co2(CO)8, 2.0 g of molecular sieves and 0.58 g (7.74 mmol) of TMANO, 0.22 g (80%) of
10 was obtained as a pale yellow oil, and following Method B, from 0.25 g (0.86 mmol) of 9,
0.35 g (1.04 mmol) of Co2(CO)8, 2.0 g of molecular sieves and 0.58 g (7.74 mmol) of
TMANO, 0.22 g (80%) of 10 was obtained.
1
H NMR CDCl3  -0.20 (s, 3H), 0.09 (s, 3H), 0.88 (s, 9H), 1.52 (td, 1H, J1= 13.2, J2= 1.1.
Hz), 2.08 (dd, 1H, J1= 13.3 Hz, J2= 2.2 Hz), 2.46-2.55 (m, 1H), 2.75 (dd, 1H, J1= 18.7 Hz, J2=
6.6 Hz), 3.56-3.65 (m, 1H), 4.77 (d, 1H, J= 13.2 Hz), 4.94 (d, 1H, J= 13.2 Hz), 5.00 (d, 1H J=
6.0 Hz), 5.97 (d, 2H, J= 2.2 Hz), 6.06 (s, 1H), 6.55 (t, 1H, J= 2.2 Hz); 13C NMR  CDCl3
208.2, 174.9, 134.3, 132.0, 122.2, 108.7, 106.5, 66.3, 49.5, 43.0, 41.8, 38.4, 25.8, 18.0, -5.3, 5.5; IR (neat)  2920, 2860, 1710 cm-1.
1
8.0
7.5
7.0
6.5
6.0
5.5
5.0
4.5
4.0
(ppm)
3.5
3.0
2.5
2.0
2.0060
1.0516
2.7107
1.0000
0.9721
2.4665
6.1095
0.7123
2.8172
2.7952
2.7531
2.7311
2.7201
2.7000
2.6945
2.6743
2.6542
2.1192
2.1119
2.0551
2.0478
1.6502
1.6044
1.5623
1.5586
3.7168
3.6984
3.6783
3.6563
3.6380
5.3070
5.2978
5.2869
5.2612
5.0432
4.9974
6.4301
7.5879
7.5623
7.3992
7.3699
7.2966
7.2728
7.2692
7.2453
7.1354
7.1098
7.0860
0.6766
0.8776
1.1710
0.8803
0.7425
Integral
Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2001
Compound 5
1.5
1.0
0.5
0.0
220
200
180
160
140
120
100
(ppm)
80
44.3912
42.9597
39.7490
38.2609
66.3892
101.9014
108.6463
141.0448
136.9364
132.0354
127.0130
122.4840
121.0445
119.8960
174.5756
208.1063
Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2001
60
40
20
0
Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2001
Compound 6.
Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2001
7.57.57.47.37.27.27.27.17.17.0
86 60 01 73 78 54 30 28 02 78
1 5 1 6 3 5 7 1 4 6
6.3 6.1
56 05
8
8
5.25.25.25.25.04.9
99 53 20 00 04 60
7 9 9 8 7 7
0.7 0.9 1.1 0.7
40 34 64 93
6 4 0 9
0.7 0.9
48 59
5
8
0.9 0.8 1.1
63 69 34
7 8 6
Int
egr
al
8.5
8.0
7.5
7.0
6.5
6.0
5.5
5.0
3.63.63.63.63.6
87 69 49 32 28
5 1 0 5 8
2.82.82.72.72.62.62.52.52.52.12.12.02.01.61.51.50.9
22 00 58 36 35 15 91 69 51 22 15 58 51 09 65 23 04
7 7 6 6 8 7 9 9 6 9 5 7 4 9 9 8 5
1.0
00
0
4.5
4.0
(ppm)
3.5
1.1 1.1
08 41
9 4
3.0
2.5
1.1
01
0
2.0
1.3
50
1
1.5
9.5
41
5
1.0
0.5
0.1
53
4
0.1
28
8
2.4
58
8
2.4
62
6
0.0
220
200
180
160
140
120
(ppm)
100
80
60
40
20
-5.0712
-5.3913
18.0035
25.6950
44.1783
42.7882
41.4235
38.4159
66.9412
101.0434
108.4654
141.2366
136.5778
131.8854
127.1087
121.9530
120.8662
119.5436
174.6059
207.8573
Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2001
0
11.0
10.0
9.0
8.0
7.0
6.0
1.6190
1.5750
1.5310
2.7275
5.0
4.0
(ppm)
3.0
1.9603
2.6229
2.6010
2.5753
5.0083
4.9680
-100.0000
2.2524
6.3640
7.5796
0.8991
Integral
7.4047
7.3790
Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2001
2.0
1.0
0.0
-1.0
-2.0
11.0
10.0
9.0
8.0
7.0
6.0
5.0
4.0
(ppm)
4.3255
2.4434
2.8300
2.8080
2.7658
2.7457
2.6229
2.6010
3.6764
-100.0000
2.3511
Integral
5.0156
4.9698
Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2001
3.0
2.0
1.0
0.0
-1.0
-2.0
10.0
9.0
8.0
7.0
6.0
(ppm)
5.0
4.0
3.0
0.9981
1.0942
2.2473
1.0000
1.0940
1.0970
0.9305
1.3560
0.7291
0.8659
1.2392
0.9570
1.4578
1.9619
Integral
3.2886
3.2684
3.2501
2.8470
2.8251
2.7848
2.7628
2.7408
2.7005
2.5594
2.5521
2.5429
2.5228
2.5136
2.5063
2.2113
2.2040
2.1490
2.1417
4.8678
4.8165
5.8645
5.8278
5.5420
5.4926
6.2034
6.1924
7.9439
7.9347
7.9274
7.9164
7.8120
7.8028
7.7955
7.7845
7.4675
7.4419
7.3906
7.3631
7.2513
7.2257
7.2000
7.0920
7.0663
7.0425
Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2001
Compound 7.
2.0
1.0
200
180
160
140
120
100
(ppm)
80
60
40
29.6434
48.2248
44.1948
42.8352
38.3798
100.2670
108.5362
138.0295
136.8442
134.4318
132.0821
131.6010
127.1317
123.6664
122.0069
120.7240
120.0407
167.5229
172.5500
206.9240
Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2001
20
0
9.0
8.5
8.0
7.5
7.0
6.5
6.0
5.5
5.0
4.5
(ppm)
4.0
3.5
3.0
2.5
2.0
1.5
1.0
8.8516
3.0578
3.2259
12.343
1.4272
1.3102
1.3946
1.0000
1.3990
1.4817
1.5284
1.1340
0.9117
1.2554
0.6612
1.1594
1.0714
Integral
0.2744
0.1608
0.0711
0.9669
3.4842
3.4750
3.4347
3.4274
3.1690
3.1617
3.1489
2.9052
2.8723
2.8558
2.8246
2.7752
2.7513
2.7147
2.6891
2.1797
2.1688
2.1193
2.1083
3.8158
3.7809
3.7681
3.7333
5.0670
5.0597
5.0377
5.0304
4.6219
4.6109
4.5761
4.5651
6.5015
7.6246
7.5989
7.3388
7.3113
7.2435
7.2398
7.2160
7.1940
7.1886
7.1409
7.1153
7.0915
Supplementary Material (ESI) for Chemical Communications
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Compund 8.
0.5
0.0
211.1005
200
180
160
140
120
100
(ppm)
80
60
40
20
-0.2265
-4.5284
-5.1072
18.1668
25.7527
46.7816
44.9060
42.8909
40.6179
67.1550
99.9044
108.6129
127.2990
121.4491
120.7589
119.6712
137.0325
143.3983
142.4710
184.1172
Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2001
210
(ppm)
0
7.5
7.0
6.5
6.0
0.7342
1.4631
5.5
5.0
4.5
4.0
3.5
(ppm)
3.0
2.5
2.0
1.5
1.0
0.5
0.0929
-0.1984
2.6180
2.7952
2.7733
2.7329
2.7110
2.5479
2.5278
2.5076
2.5039
2.4838
2.4655
2.1174
2.1100
2.0532
2.0459
1.5641
1.5604
1.5201
1.4798
1.4761
0.8807
3.6472
3.6288
3.6087
3.5885
3.5684
2.7198
10.289
1.1281
1.1428
1.2536
1.1607
1.0000
0.8908
1.0644
1.2454
6.0618
5.9739
5.9666
0.7870
5.0175
4.9974
4.9699
4.9259
4.7922
4.7482
6.5565
6.5492
6.5418
Integral
Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2001
Compound 10.
0.0
200
180
160
140
120
100
(ppm)
80
60
40
20
-5.3163
-5.4837
18.0482
25.7737
43.0164
41.7684
38.4007
49.4729
66.3183
108.7175
106.4654
122.1673
134.3272
131.9705
174.8788
208.2348
Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2001
0