A. de Meijere et al.
(Cquat, C-4), 182.8 (Cquat, C-1); IR (film): n˜ =3063, 1708 (C=O), 1646,
1613, 1456, 1383 cmÀ1; MS (70 eV): m/z (%): 521 (9) [M +], 476 (4) [M +
ÀC2H5O], 430 (100) [M +ÀC7H7], 340 (37), 179 (5), 169 (18), 141 (25),
131 (66), 91 (99) [C7H7+], 73 (49) [C3H9Si+], 43 (5) [C3H7+]; HRMS
(EI): m/z: calcd for C31H43NO4Si: 521.2961 (correct HRMS).
2-[1’-(tert-Butyldimethylsilyloxy)ethyl]-4-ethoxy-5,7-diphenylcyclopen-
ta[b]pyran (4g-Ph) and 2-[1’-(tert-butyldimethylsilyloxy)ethyl]-4-ethoxy-
5,6-diphenylcyclopenta[b]-pyran (8g-Ph): Variant A: Following GP 2,
complex (E)-2ga (180 mg, 0.38 mmol) in THF (8 mL) was treated with
phenylethyne (311 mg, 3.04 mmol) and the mixture was heated for 37 h.
After chromatography [20 g silica gel, elution with pentane/Et2O (5:1)]
8g-Ph (Rf =0.45) and 4g-Ph (Rf =0.39) were obtained as a red oil (25 mg,
14%) and as red crystals (48 mg, 27%), m.p. 1388C. 8g-Ph: 1H NMR
(250 MHz, CDCl3): d=À0.10 [s, 6H, Si(CH3)2], 0.81 [s, 9H, SiC(CH3)3],
1.18 (d, 3J=7.2 Hz, 3H, CHCH3), 1.58 (t, 3J=7.0 Hz, 3H, OCH2CH3),
4.44 (m, 2H, OCH2CH3), 5.20 (q, 3J=7.2 Hz, 1H, CHCH3), 6.07 (s, 1H,
7-H), 7.14 (s, 1H, 3-H), 7.30–7.47 (m, 8H, Ph-H), 7.80–7.88 (m, 2H, Ph-
H); 13C NMR (62.9 MHz, CDCl3, plus DEPT): d=À5.0, À4.9 (+,
SiCH3), 14.5 (+, OCH2CH3), 18.1 [Cquat, SiC(CH3)3], 25.4 (+, CHCH3),
25.8 [+, SiC(CH3)3], 65.6 (+, CHCH3), 65.7 (À, OCH2CH3), 80.6 (+, C-
7), 107.5, 117.5, 119.0 (Cquat, C-4a,5,6), 124.6, 125.5, 126.2, 126.4, 127.9,
128.6, 130.2 (+, C-Ph, C-3), 135.0, 139.8ꢃ2, 157.1, 162.6 (Cquat, C-Ph, C-
2-[1’-(tert-Butyldiphenylsilyloxy)ethyl]-4-ethoxy-5,7-diphenylcyclopen-
ta[b]pyran (4 f-Ph) and 2-[1’-(tert-butyldiphenylsilyloxy)ethyl]-4-ethoxy-
5,6-diphenylcyclopenta[b]pyran (8 f-Ph): Variant A: Following GP 2,
complex (E)-2 fa (411 mg, 0.68 mmol) in THF (14 mL) was treated with
phenylethyne (556 mg, 5.44 mmol), and the mixture was heated for 39 h.
After chromatography [30 g silica gel, elution with pentane/Et2O (5:1)],
8 f-Ph (8 mg, 2%; Rf =0.62) and 4 f-Ph (160 mg, 39%; Rf =0.39) were ob-
tained as red oils. 8 f-Ph: 1H NMR (250 MHz, CDCl3): d=1.02 (d, 3J=
7.2 Hz, 3H, CHCH3), 1.07 [s, 9H, SiC(CH3)3], 1.56 (t, 3J=7.0 Hz, 3H,
OCH2CH3), 4.42 (m, 2H, OCH2CH3), 5.31 (q, 3J=7.2 Hz, 1H, CHCH3),
6.27 (s, 1H, 7-H), 6.98–7.50 (m, 19H, 3-H, Ph-H), 7.79–7.84 (m, 2H, Ph-
H); 13C NMR (62.9 MHz, CDCl3, plus DEPT): d=14.5 (+, OCH2CH3),
19.1 [Cquat, SiC(CH3)3], 25.1 (+, CHCH3), 26.9 [+, SiC(CH3)3], 65.6 (À,
OCH2CH3), 66.7 (+, CHCH3), 80.5 (+, C-7), 107.5, 119.2 (Cquat, C-5,6),
124.5, 125.4, 125.8, 126.1, 126.7, 127.5, 127.6, 127.7, 128.1, 128.5, 128.7,
129.6, 129.7 (+, C-3, C-Ph), 133.7, 135.0, 135.6, 135.6 (Cquat, C-Ph), 139.3,
142.6, 156.4, 162.6 (Cquat, C-2,4,4a,7a).
Compound 4 f-Ph: 1H NMR (250 MHz, CDCl3): d=1.15 [s, 9H, SiC-
(CH3)3], 1.32 (t, 3J=7.0 Hz, 3H, OCH2CH3), 1.57 (d, 3J=7.2 Hz, 3H,
CHCH3), 4.11 (m, 2H, OCH2CH3), 4.94 (q, 3J=7.2 Hz, 1H, CHCH3),
6.52 (s, 1H, 6-H), 7.04–7.43 (m, 13H, 3-H, Ph-H), 7.53–7.68 (m, 4H, Ph-
H), 7.70–7.76 (m, 2H, Ph-H), 7.79–7.85 (m, 2H, Ph-H); 13C NMR
(62.9 MHz, CDCl3, plus DEPT): d=14.4 (+, OCH2CH3), 19.2 [Cquat, SiC-
(CH3)3], 23.4 (+, CHCH3), 26.9 [+, SiC(CH3)3], 64.7 (À, OCH2CH3),
69.3 (+, CHCH3), 91.7 (+, C-6), 107.5, 117.0 (Cquat, C-5,7), 124.1, 124.5,
124.8, 125.4, 127.4, 127.7, 127.8, 128.2, 128.4, 128.6, 129.1, 129.9, 130.1 (+,
C-3, C-Ph), 132.8, 133.0, 135.5, 135.7 (Cquat, C-Ph), 138.3, 148.2, 160.3,
166.7 (Cquat, C-2,4,4a,7a); IR (film): n˜ =3032, 2926, 2842, 1631, 1599,
1500 cmÀ1; MS (70 eV): m/z (%): 596 (100) [M +], 539 (1) [M +ÀC4H9],
199 (22), 111 (17), 97 (23), 85 (26), 71 (38), 57 (68) [C4H9+]; HRMS (EI):
m/z: calcd for C40H40O3Si: 596.2746 (correct HRMS).
2,4,7a); IR (film): n˜ =3064, 3050, 2980, 1625, 1593, 1530, 1490, 1448 cmÀ1
;
MS (70 eV): m/z (%): 472 (100) [M +], 73 (26); HRMS (EI): m/z: calcd
for C30H36O3Si: calcd for 472.2433 (correct HRMS).
Compound 4g-Ph: 1H NMR (250 MHz, CDCl3): d=0.15 (s, 3H, SiCH3),
0.20 (s, 3H, SiCH3), 0.98 [s, 9H, SiC(CH3)3], 1.44 (t, 3J=7.0 Hz, 3H,
OCH2CH3), 1.63 (d, 3J=7.2 Hz, 3H, CHCH3), 4.32 (m, 2H, OCH2CH3),
4.95 (q, 3J=7.2 Hz, 1H, CHCH3), 6.63 (s, 1H, 6-H), 7.11–7.25 (m, 2H,
Ph-H), 7.31 (s, 1H, 3-H), 7.33–7.42 (m, 4H, Ph-H), 7.62–7.70 (m, 2H, Ph-
H), 7.83–7.91 (m, 2H, Ph-H); 13C NMR (62.9 MHz, CDCl3, plus DEPT):
d=À5.0, À4.8 (+, SiCH3), 14.5 (+, OCH2CH3), 18.1 [Cquat, SiC(CH3)3],
23.9 (+, CHCH3), 25.7 [+, SiC(CH3)3], 64.9 (À, OCH2CH3), 68.2 (+,
CHCH3), 91.0 (+, C-6), 107.5, 117.2, 117.4 (Cquat, C-4a,5,7), 124.2, 124.5,
124.8, 125.5, 127.4, 128.5, 129.2 (+, C-Ph, C-3), 135.6, 138.4 (Cquat, C-Ph),
147.3, 160.7, 168.0 (Cquat, C-2,4,7a); IR (KBr): n˜ =3060, 3039, 3007, 2837,
1622, 1590, 1560, 1491 cmÀ1; MS (70 eV): m/z (%): 472 (59) [M +], 453
(11), 408 (4), 396 (7), 362 (53), 316 (8), 259 (5), 230 (10), 202 (11), 156
(9), 111 (11), 97 (17), 91 (100), 73 (70), 57 (46) [C4H9+], 43 (47); HRMS
(EI): m/z: calcd for C30H36O3Si: 472.2433 (correct HRMS).
Variant B: According to GP2, complex [(E)-2gb] (85 mg, 0.14 mmol) in
THF (3 mL) was treated with phenylethyne (114 mg, 1.12 mmol), and the
mixture was heated for 26 h. Compounds 8g-Ph (15 mg, 23%) and 4g-Ph
(27 mg, 41%) were obtained after chromatography on silica gel (10 g).
Variant B: According to GP 2, complex (E)-2 fb (280 mg, 0.37 mmol) in
THF (8 mL) was treated with phenylethyne (302 mg, 2.96 mmol), and the
mixture was heated for 16 h. 8 f-Ph (49 mg, 22%) and 4 f-Ph (163 mg,
74%) were obtained after chromatography on silica gel (15 g).
2-[1’-(tert-Butyldimethylsilyloxy)ethyl]-4-ethoxy-5,7-di-n-propylcyclopen-
ta[b]pyran (4g-nPr): According to GP 2, complex (E)-2gb (85 mg,
0.14 mmol) in THF (3 mL) was treated with 1-pentyne (76 mg,
1.12 mmol), and the mixture was heated for 4 d. After column chroma-
tography [10 g silica gel, elution with pentane/Et2O (10:1)], 4g-nPr (Rf =
2-[1’-(tert-Butyldiphenylsilyloxy)ethyl]-4-ethoxy-5,7-di-n-propylcyclopen-
ta[b]pyran (4 f-nPr): Variant A: According to GP 2, complex (E)-2 fa
(300 mg, 0.50 mmol) in THF (10 mL) was treated with 1-pentyne
(272 mg, 4.00 mmol), and the mixture was heated for 2 d. After chroma-
tography [30 g silica gel, elution with pentane/Et2O (10:1)], 4 f-nPr (Rf =
0.51) was obtained as red crystals (33 mg, 13%). M.p. 1348C; 1H NMR
0.51) was obtained as
a
red oil (6 mg, 11%). 1H NMR (250 MHz,
CDCl3): d=0.09 (s, 3H, SiCH3), 0.13 (s, 3H, SiCH3), 0.72–1.04 (m, 9H,
OCH2CH3, CH2CH2CH3), 1.28 [s, 9H, SiC(CH3)3], 1.49 (d, 3J=7.1 Hz,
3H, CHCH3), 1.52–1.74 (m, 4H, CH2CH2CH3), 2.58 (t, 3J=7.2 Hz, 2H,
CH2CH2CH3), 2.74 (t, 3J=7.2 Hz, 2H, CH2CH2CH3), 4.28 (m, 2H,
OCH2CH3), 4.79 (q, 3J=7.1 Hz, 1H, CHCH3), 6.37 (s, 1H, 6-H), 6.42 (s,
1H, 3-H); IR (film): n˜ =2938, 2904, 2839, 1635, 1598, 1523, 1450,
1364 cmÀ1; MS (70 eV): m/z (%): 404 (20) [M +], 375 (37) [M +ÀC2H5],
206 (21), 108 (19), 80 (39), 52 (100); HRMS (EI): m/z: calcd for
C24H40O3Si: 404.2746 (correct HRMS).
3
3
(250 MHz, CDCl3): d=0.90 (t, J=7.1 Hz, 3H, CH2CH2CH3), 0.96 (t, J=
7.1 Hz, 3H, CH2CH2CH3), 1.22 [s, 9H, SiC(CH3)3], 1.41 (t, 3J=7.0 Hz,
3H, OCH2CH3), 1.45 (d, 3J=7.2 Hz, 3H, CHCH3), 1.51–1.54 (m, 4H,
CH2CH2CH3), 2.51 (t, 3J=7.1 Hz, 2H, CH2CH2CH3), 2.55 (t, 3J=7.1 Hz,
2H, CH2CH2CH3), 4.30 (m, 2H, OCH2CH3), 4.75 (q, 3J=7.2 Hz, 1H,
CHCH3), 6.32 (s, 1H, 6-H), 6.44 (s, 1H, 3-H), 7.25–7.50 (m, 6H, Ph-H),
7.55–7.64 (m, 2H, Ph-H), 7.66–7.75 (m, 2H, Ph-H); 13C NMR (62.9 MHz,
CDCl3, plus DEPT): d=14.2, 14.3, 14.9 (+, CH2CH2CH3, OCH2CH3),
19.3 [Cquat, SiC(CH3)3], 23.3 (+, CHCH3), 24.3, 25.1 (À, CH2CH2CH3),
26.9 [+, SiC(CH3)3], 27.4, 31.7 (À, CH2CH2CH3), 64.0 (À, OCH2CH3),
69.3 (+, CHCH3), 89.9 (+, C-6), 105.0, 109.2, 115.1 (Cquat, C-4a,5,7),
124.7 (+, C-3), 125.4 (Cquat, C-7a), 127.7, 127.8, 129.8, 129.9 (+, C-Ph),
133.1, 133.5 (Cquat, C-Ph), 135.7, 135.8 (+, C-Ph), 158.2, 165.6 (Cquat, C-
2,4); IR (KBr): n˜ =3064, 3041, 2954, 2925, 1642, 1606 cmÀ1; MS (70 eV):
m/z (%): 528 (18) [M +], 499 (24) [M +ÀC2H5], 327 (16), 306 (5), 256
(17), 206 (100), 199 (54); HRMS (EI): m/z: calcd for C34H44O3Si:
528.3059 (correct HRMS).
4-Ethoxy-5,6-diphenyl-2-[1’-(trimethylsilyloxy)ethyl]cyclopenta[b]pyran
(8h-Ph): According to GP 2, complex (E)-2hb (1.50 g, 2.55 mmol) in
THF (50 mL) was treated with phenylethyne (2.08 g, 20.4 mmol), and the
mixture was heated for 12 h. After chromatography [150 g silica gel, elu-
tion with pentane/Et2O (10:1)], 8h-Ph (Rf =0.44) was obtained as a red
oil (230 mg, 21%). 1H NMR (250 MHz, CDCl3): d=À0.03 [s, 9H, Si-
(CH3)3], 1.19 (d, 3J=7.0 Hz, 3H, CHCH3), 1.56 (t, 3J=7.0 Hz, 3H,
3
3
OCH2CH3), 4.42 (q, J=7.0 Hz, 2H, OCH2CH3), 5.20 (q, J=7.0 Hz, 1H,
CHCH3), 6.01 (s, 1H, 7-H), 7.18 (s, 1H, 3-H), 7.31–7.46 (m, 8H, Ph-H),
7.80–7.88 (m, 2H, Ph-H); 13C NMR (62.9 MHz, CDCl3, plus DEPT): d=
À0.2 [+, Si(CH3)3], 14.5 (+, OCH2CH3), 25.2 (+, CHCH3), 65.1 (+,
CHCH3), 65.7 (À, OCH2CH3), 80.6 (+, C-7), 107.6, 117.6, 119.0 (Cquat, C-
4a,5,6), 124.6, 125.5, 126.2, 126.3, 127.8, 128.5, 130.1 (+, C-3, C-Ph),
135.0, 139.8 (Cquat, C-Ph), 143.2, 156.7, 162.6 (Cquat, C-2,4,7a); IR (film):
Variant B: According to GP 2, complex (E)-2 fb (233 mg, 0.31 mmol) in
THF (6 mL) was treated with 1-pentyne (169 mg, 2.48 mmol), and the
mixture was heated for 35 h. Compound 4 f-nPr (38 mg, 23%) was ob-
tained after chromatography on silica gel (20 g).
4144
ꢂ 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2005, 11, 4132 – 4148