Tetrahydroindenes and Hexahydroazulenes
700±710
diastereotopic 9-OCH2), 3.92 and 3.65 (each 1H, each m, diastereotopic 11-
OCH2), 3.84 and 3.57 (each 1H, each m, diastereotopic 13-OCH2), 3.11 (dd,
1H; 8-H), 2.88 (dd, 1H; 21-H), 2.38 (dd, 1H; 14-H), 2.46 (m, 1H; 4-Heq),
1.46 (m, 1H; 4-Hax), 2.30 (m, 1H; 7-Heq), 1,35 (m, 1H; 7-Hax); 1.25 and 0.85,
1.30, and 1.02 (1H each, diastereotopic 6-H2 and 5-H2); 2.38 and 1.49, 2.02
and 1.28, 1.64 and 1.08, 1.54 and 1.28 (1H each, diastereotopic 22-H2 ± 25-
H2); 2.24 and 1.64, 1.95 and 1.54, 1.64 and 1.39, 1.69 and 1.09 (1H each,
diastereotopic 15-H2 ± 18-H2); 1.37, 1.30, and 1.22 (3H each, each t, each
CH3CH2O); 13C NMR (C6D6): d 164.2 (Cq, PhCO), 163.2 and 158.8 (each
Cq, C12, C20), 156.9 (Cq, C9), 156.2 (Cq, C26); 142.4, 124.7, and 116.7 (each
Cq, C2, C9, C10); 133.8, 129.7, and 128.7 (each CH, Ph), 130.9 (i-C Ph),
114.8 (CH, C27), 96.2 (Cq, C11), 94.0 (Cq, C13), 76.4 (CH, C14); 69.2, 62.3,
and 61.4 (each CH2O), 66.5 (CH, C21), 57.5 (CH, C8), 57.2 (Cq, C19), 53.6
(Cq, C1), 31.8 (CH2, C7), 27.8 (CH2, C4), 28.6 and 25.3 (each CH2, C6 and
C5); 27.1, 26.0, 24.9, and 23.9 (each CH2, C15 ± C18); 25.6, 24.6, 23.2, and
1H; 8-H), 2.97 (dd, 1H; 21-H), 2.51 (dd, 1H; 14-H), 2.68 (m, 1H; 4-Heq),
1.76 (m, 1H; 4-Hax), 2.47(m, 1H; 7-Heq), 1,28 (m, 1H; 7-Hax); 1.72 and 1.15,
1.68 and 1.10 (each m, each 1H; diastereotopic 6-H2 and 5-H2); 2.16 and
1.69, 2.42 and 1.44, 1.62 and 1.24, 1.58 and 1.18 (each m, each 1H,
diastereotopic 22-H2 ± 25-H); 2.48 and 1.64, 2.41 and 1.55, 1.68 and 1.54, 1.66
and 1.12 (each m, each 1H; diastereotopic 15-H2 ± 18-H2), 1.27, 1.19, and
1.16 (each t, each 3H; each CH3CH2O); 13C NMR (C6D6): d 166.6 (Cq,
PhO), 163.9 and 159.7 (each Cq, C12 and C20), 157.4 (Cq, C9), 154.9 (Cq,
C26); 143.2, 128.3, and 123.7 (each Cq, C2, C3, and C10); 129.5, 124.0, and
119.8 (each CH, Ph), 103.0 (CH, C27), 95.7 (Cq, C13), 93.8 (Cq, C11), 77.7
(CH, C14); 69.0, 62.1, and 61.6 (each OCH2), 68.0 (CH, C21), 58.0 (CH,
C8), 56.9 (Cq, C19), 53.7 (Cq, C1), 32.3 (CH2, C4), 26.3 (CH2, C7), 28.9 and
25.2 (each CH2, C6 and C5); 27.8, 24.6, 24.0, and 23.5 (each CH2, C15 ±
C18); 25.8, 24.5, 23.3, and 22.4 (each CH2, C22 ± C25); 16.0, 15.6, and 15.5
(each CH3CH2O); MS (70 eV): m/z (%): 580 (100) [M] , 551 (95) [M
22.5 (each CH2, C22 ± C25); 16.0, 15.9, and 15.6 (each CH3CH2O); IR
Et] , 535 (55) [M EtO] , 487 (86) [M PhO] ; elemental analysis calcd
1
(hexane): nÄ 1744 cm (80%) (n(C O)); MS (70 eV): m/z (%): 608 (10)
(%) for C39H48O4 (580.8): C 80.57, H 8.26; found: C 80.24, H 8.06.
[M] , 579 (5) [M Et] , 503 (9) [M PhCO] ; elemental analysis calcd
4-Acetoxy-1,1,1,1,1-pentacarbonyl-2-ethoxy-4-phenyl-1-tungsta-1,3-buta-
diene (15) and (1S*,4R*,7R*)-4-acetoxy-3-(1,1,1,1,1-pentacarbonyl-2-
ethoxy-1-tungsta-2-ethenyl)-6-ethoxy-2-phenyl-spiro-tricyclo[5.4.01.4.01,7]-
undeca-2,5-diene (16): A mixture of pentacarbonyl(3-cyclohex-1-enyl-1-
ethoxy-2-propyn-1-ylidene)tungsten (1b, 243 mg, 0.50 mmol) and penta-
carbonyl(1-ethoxy-3-phenyl-2-propyn-1-ylidene)tungsten (14, 241 mg,
0.50 mmol) in n-pentane (1 mL) was treated with acetic acid (2a, 60 mg,
1.00 mmol) and triethylamine (100 mg, 0.80 mmol) in diethyl ether (1 mL)
in a 2 mL screw-top vessel for 4 h at 20oC. Flash column chromatography
gave a red fraction containing compounds 11a, 11'a, and 16 and a brown
fraction containing compound 15. Compound 16 was isolated by crystal-
lization from diethyl ether/n-pentane at 20oC (61 mg, 35%, Rf 0.8 in n-
pentane/diethyl ether (10:1), m.p. 108oC). Compound 15, in the brown
fraction, was identified by comparison of its spectroscopic data with
literature values.[17]
(%) for C40H48O5 (608.8): C 78.91, H 7.95; found: C 78.22, H 8.03.
Compounds 13b (13'b): 1H NMR (600 MHz, C6H6):[16] d 8.29 [8.30] (m,
3
2H; o-H Ph), 7.19 [7.19] (m, 3H; m- and p-H Ph), 6.66 [6.52] (dt, J 10.1
4
3
[9.8] Hz, J 2.0 [2.1] Hz, 1H; 2-H), 5.73 [5.71] (dt, J 10.1 [9.8] and 4.3
[4.4] Hz, 1H; 1-H), 5.60 [5.66] (d, 3J 7.1 [7.4] Hz, 1H; 3'-H), 5.18 [5.32] (d,
3J 7.1 [7.4] Hz, 1H; 2'-H), 3.16 [3.17] (q, 2H; OCH2), 2.34 [2.41] (t, 2H;
4-H), 1.89 [1.94] (m, 2H; 6-H), 1.55 [1.55] (m, 2H; 5-H), 0.57 [0.59] (t, 3H;
CH3CH2O); 13C NMR (C6D6): d 163.9 [164.1] (Cq, PhCO), 145.9 [145.5]
(Cq, C3'), 139.1 [140.7] (Cq, C1'), 132.5 [132.5] (CH, C1), 128.1 [128.1] (CH,
C2), 122.1 [123.2] (Cq, C3); 133.4, 130.5, and 128.3 [132.6, 130.5, and 128.4]
(each CH, Ph), 130.1 [129.2] (i-C Ph), 98.4 [97.7] (CH, C2'), 69.0 [68.9]
(OCH2), 25.8 [26.1] (CH2, C4), 25.6 [25.8] (CH2, C6), 22.6 [22.3] (CH2, C5),
1
14.7 [14.7] (CH3CH2O); IR (hexane): nÄ 1742 cm (60%) (n(C O)).
(1S*,8R*,11R*,12S*)-9,11-Diethoxy-17-phenoxypentacyclo-
[9.5.2.01,12.02,10.03,8]octadeca-2,9,17-triene (11c), (1S*,8S*,11R*,12S*)-
9,11-diethoxy-17-phenoxypentacyclo[9.5.2.01,12.02,10.03,8]octadeca-2,9,17-tri-
ene (11'c), and (1S*,8R*,11S*,13S*,14R*,19S*,21R*)-9,11,13-triethoxy-
26-phenoxyoctacyclo[9.9.5.2.01,21.02,10.03,8.012,20.014,19]heptacosa-2,9,12,26-tet-
raene (12c): Pentacarbonyl (3-cyclohex-1-enyl-1-ethoxy-2-propyn-1-ylide-
ne)tungsten (1b, 243 mg, 0.50 mmol ) and phenol (2c, 47 mg, 0.50 mmol)
were treated in the presence of triethylamine (50 mg, 0.50 mmol) in
benzene (2 mL) as described above, over 12 h, to give compounds 11c and
11'c (55 mg, 53%, 11c:11'c 10:7, Rf 0.5 in n-pentane/diethyl ether
(10:1)) and compound 12c (20 mg, 21%, Rf 0.3 in n-pentane/diethyl ether
(10:1)). Treatment of compounds 1b and 2c in a molar ratio of 1:1 in
benzene at 20oC gave a product ratio of 11c:11'c:12c 10:7:5. Application
of a molar ratio of 2:1 gave 11c:11'c:12c 10:5:15.
Compound 16: 1H NMR (C6D6): d 7.23, 7.19, and 7.08 (2:2:1H; Ph), 5.62
(s, 1H; 5-H), 4.50 (br, 2H; diastereotopic W C-OCH2), 3.75 and 3.60 (each
m, each 1H; diastereotopic 6-OCH2), 3.09 (dd, 1H; 7-H), 2.14 (m, 2H),
1.91 ± 1.57 (m, 4H), 1.44 (m, 2H), 1.75 (s, 3H; CH3CO), 1.20 and 1.04 (each
t, each 3H, each OCH2CH3); 13C NMR (C6D6): d 319.2 (br, W C), 204.3
and 198.0 (each Cq, trans- and cis-CO of W(CO)5), 170.4 (Cq, CH3CO),
166.1 (Cq, C6), 154.4 (Cq, C3), 135.9 and 131.8 (each Cq, i-C Ph and C2);
129.0, 128.9, and 123.0 (each CH, Ph), 96.9 (CH, C5), 91.9 (Cq, C4), 79.2
Compounds 11c [11'c]: 1H NMR (600 MHz, C6D6):[16] d 7.05, 6.98, and
6.81 [7.07, 7.02, and 6.82] (2:2:1H; Ph), 5.05 [5.05] (s, 1H; 18-H), 4.11 and
3.98 [4.13 and 3.99] (each m, each 1H, diastereotopic 9-OCH2), 3.65 and
3.43 [3.66 and 3.42] (each m, each 1H, diastereotopic 11-OCH2), 3.06 [3.11]
(dd, 1H; 8-H), 2.55 [2.61] (dd, 1H; 12-H), 2.68 [2.64] (m, 1H; 4-Heq), 2.03
[2.03] (m, 1H; 4-Hax), 2.50 [2.39] (m, 1H; 7-Heq), 1.33 [1.23] (m, 1H; 7-Hax);
1.73 and 1.17, 1.66 and 1.18 [1.73 and 1.16, 1.67 and 1.19] (each 1H,
diastereotopic 6-H2 and 5-H2); 2.62 and 1.66, 1.84 and 1.62, 1.63 and 1.18,
161 and 1.13 [2.63 and 1.65, 1.81 and 1.62, 1.62 and 1.01, 1.58 and 1.09] (each
1H, diastereotopic 13-H2 ± 16-H2), 1.18 and 1.11 [1.17 and 1.10] (each t, each
3H; each CH3CH2O); 13C NMR (C6D6): d 163.5 [163.2] (i-C PhO), 156.8
[157.6] (Cq, C17), 150.7 [150.6] (Cq, C9); 143.6, 123.0, and 122.4 [143.7,
123.5, and 121.8] (each Cq, C2, C3, and C10); 129.7, 124.3, and 120.4 [129.7,
124.1, and 119.9] (each CH, Ph), 107.3 [105.4] (CH, C18), 90.8 [90.8] (Cq,
C11), 68.3 [69.3] (CH, C12), 68.1 [68.1] (9-OCH2), 60.9 [60.9] (11-OCH2),
57.5 [56.7] (CH, C8), 53.2 [53.2] (Cq, C1), 32.3 [31.9] (CH2, C7), 26.4 [26.6]
(each CH2, C4), 29.0 and 25.7 [29.4 and 25.7] (each CH2, C6 and C5); 25.1,
24.5, 23.7, and 23.0 [24.9, 24.4, 23.7, and 22.8] (each CH2, C13 ± C16), 15.7
and 15.5 [15.7 and 15.5] (each CH3CH2O); MS (70 eV): m/z (%): 418 (100)
(dynamically broadened W C-OCH2), 65.3 (6-OCH2), 54.0 (Cq, C1), 43.2
(CH, C7); 24.9, 23.4, 19.1, and 17.9 (each CH2, C8 ± C11), 21.0 (CH3CO),
14.5 (2 Â OCH2CH3); IR (hexane) (cm 1 (%) ): nÄ 2065.4 (30), 1940.2 (90),
and 1917.1 (100) (n(C O)); 1767 (70) (n(C O)); MS (70 eV), m/z 184W (%):
704 (20) [M] , 620 (30) [M 3 Â CO] , 592 (89) [M 4 Â CO] ; elemental
ꢀ
analysis calcd (%) for C29H28O9W (704.4): C 49.43, H 3.98; found: C 49.76,
H 4.07. X-ray crystal structure analysis of compound 16 (code 1194.aum),
1
formula C29H28O9W, Mr 704.36 gmol
,
orange crystal 0.25 Â 0.20 Â
0.10 mm, a 10.908(1), b 15.818(1), c 17.327(1) , b 107.59(1)o, V
2849.9(4) 3, 1calcd 1.642 g cm
,
m 41.05 cm
, empirical absorption
3
1
correction by SORTAV (0.427 ꢁ Tꢁ 0.684), Z 4, monoclinic, space group
P21/n (no. 14), l 0.71073 , T 198 K, w and f scans, 11642 reflections
collected (Æh, Æk, Æl), [(sinq)/l] 0.65 1, 6507 independent (Rint
0.017) and 5876 observed reflections [I ꢂ 2s(I)], 355 refined parameters,
R 0.017, wR2 0.039, max. residual electron density 0.45 ( 0.88) e
,
3
hydrogens calculated and refined as riding atoms.[15]
(1S*,3R*,8R*,9R*,11R*,12R*)-18-Acetoxy-9,11-diethoxy-19-(1,1,1,1,1-
pentacarbonyl-2-ethoxy-1-tungsta-2-ethenyl)-20-phenylhexacyclo-
[M] , 389 (64) [M Et] , 325 (84) [M PhO] ; HRMS: calcd for
C28H34O3: 418.25079; found 418.25187.
[9.5.217,18.219,20.01,12.02,10.03,8]eicosa-2,17,19-triene (17a) and (1S*,12R*,13R*)-
19-Acetoxy-10,12-diethoxy-9-(phenylacetyl)pentacyclo[10.5.2.01,13.02,11.03,8]-
nonadeca-2,8,10,18-tetraene (19a): Pentacarbonyl-(1-ethoxy-3-phenyl-2-
propyn-1-ylidene)-tungsten (14, 120 mg, 0.25 mmol) was treated with
compound 11a (96 mg, 0.25 mmol) in benzene (2 mL) for 24 h at 20oC.
Compound 12c: 1H NMR (600 MHz, C6D6):[16] d 7.16, 7.08, and 6.86
(2:2:1H; Ph), 5.15 (s, 1H; 27-H), 4.17 and 4.03 (each m, each 1H;
diastereotopic 9-OCH2), 3.90 and 3.63 (each m, each 1H; diastereotopic 11-
OCH2), 4.17 and 4.03 (each m, each 1H; diastereotopic 13-OCH2), 3.03 (dd,
Chem. Eur. J. 2001, 7, No. 3
ꢀ WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2001
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707