A. F¸rstner et al.
FULL PAPER
Representative procedure for ring closing alkyne metathesis (RCAM)
(Z)-4,9-Dimethyl-2-oxo-1-oxacyclotetradec-3-ene-7-yne (38): 1H NMR
(CD2Cl2, 300 MHz): d 5.78 (s, 1H), 4.55 4.45 (m, 1H), 4.12 4.03(m,
1H), 3.34 3.22 (m, 1H), 2.60 2.50 (m, 1H), 2.48 2.30 (m, 3H), 1.85 (s,
3H), 1.80 1.20 (m, 8H), 1.09 (d, J 6.8 Hz, 3H); 13C NMR (CD2Cl2,
75 MHz): d 166.9, 155.9, 119.0, 85.6, 78.7, 62.8, 37.4, 31.0, 28.2, 26.5, 25.9,
23.4, 22.3, 17.3; MS (EI): m/z (%): 234 (15), 219 (11), 206 (96), 190 (24), 175
(40), 161 (38), 147 (100), 133 (48), 119 (78), 105 (79), 93 (74), 79 (58), 67
(34), 55 (67), 41 (99); IR: n 2963, 2917, 2861, 1719, 1653, 1451, 1385, 1333,
1247, 1164, 1136, 1058, 850, 597 cmÀ1; HR-MS (C15H22O2): calcd 234.1620,
found 234.1616; elemental analysis calcd (%) for C15H22O2 (234.16): C
76.88, H 9.46; found C 76.78, H 9.38.
9-(Phenylsulfonyl)-cyclooctadecyne (40): M.p. 87 888C; 1H NMR
(CD2Cl2, 300 MHz): d 7.88 (d, J 7.9 Hz, 2H), 7.74 7.56 (m, 3H),
2.99 2.90 (m, 1H), 2.16 (m, 4H), 1.88 1.60 (m, 4H), 1.59 1.20 (m, 22H);
13C NMR (CD2Cl2, 75 MHz): d 138.8, 133.8, 129.5, 129.0, 80.8, 80.7, 64.2,
29.3, 29.1, 29.0, 28.9, 28.7, 28.7, 28.4, 28.0, 27.6, 27.3, 26.4, 26.1, 25.0, 18.9,
18.8; MS (EI): m/z (%): 388 (7), 246 (30), 143 (29), 123 (21), 109 (51), 95
(100), 81 (96), 67 (79), 55 (65), 41 (51); IR: n 2936, 2854, 1461, 1446, 1305,
1289, 1141, 1084, 735, 692, 583, 549 cmÀ1; HR-MS (C24H36O2S): calcd
388.2436, found 388.2435.
1-(N-4'-Methoxybenzyl)-azacycloheptadec-12-yne-2-one (42): 1H NMR
(CD2Cl2, 300 MHz, rotamers): d 7.16 (d, J 12.8 Hz, 1H), 7.13(d, J
12.8 Hz, 1H), 6.89 (d, J 13.2 Hz, 1H), 6.85 (d, J 13.2 Hz, 1H), 4.52 (s,
2H), 3.80 (d, J 2.7 Hz, 3H), 3.36 (t, J 7.7 Hz, 1H), 3.22 (t, J 7.7 Hz,
1H), 2.41 (t, J 7.2 Hz, 1H), 2.38 (m, 1H), 2.20 (m, 4H), 1.80 1.56 (m,
4H), 1.53 1.30 (m, 14H); 13C NMR (CD2Cl2, 75 MHz, rotamers): d
173.0, 172.8, 159.3, 157.0, 130.9, 129.5, 128.1, 114.5, 114.2, 81.0, 80.0, 55.6,
50.6, 48.0, 47.3, 31.7, 29.8, 29.1, 28.4, 28.2, 28.0, 27.9, 27.5, 27.1, 27.1, 24.4, 19.2,
18.9, 18.8; MS (EI): m/z (%): 369 (23), 248 (11), 199 (1), 162 (2), 136 (12),
134 (2), 121 (100), 91 (3), 77 (4), 55 (5); IR: n 3072, 2928, 2856, 1644, 1612,
1512, 1460, 1441, 1417, 1247, 1175, 1035, 817 cmÀ1; elemental analysis calcd
(%) for C24H35NO2 (369.27): C 78.00, H 9.55, N 3.79; found C 77.84, H 9.38,
N 3.75.
Preparation of 7,8,11,12-tetrahydro-6,13-dioxa-1-azabenzocyclododec-9-
yne-5,14-dione (28): CH2Cl2 (160 mL) and bis(3-pentyn-1-yl) ester 27
(511 mg, 1.70 mmol) were successively added to a stirred solution of
complex 1a (104.4 mg, 0.17 mmol) in toluene (80 mL) and the resulting
mixture was stirred at 808C for 20 h. For work-up, the solvent was
evaporated and the residue was purified by flash chromatography (hexane/
EtOAc 4:1), thus affording cycloalkyne 28 as a colorless syrup (369 mg,
88%). M.p. 96 978C; 1H NMR (CDCl3, 300 MHz): d 8.76 (dd, J 1.9,
4.9 Hz, 1H), 8.12 (dd, J 1.5, 7.9 Hz, 4H), 7.52 (dd, J 7.8 Hz, 1H), 4.63(t,
J 5.5 Hz, 2H), 4.42 (t, J 5.6 Hz, 2H), 2.57 (m, 4H); 13C NMR (CDCl3,
75 MHz): d 166.1, 165.8, 151.1, 151.0, 137.1, 128.7, 125.1, 79.2, 78.8, 63.4,
63.1, 20.0, 19.4; MS (EI): m/z (%): 245 (2), 227 (3), 199 (8), 187 (2), 172 (2),
150 (2), 143(6), 122 (5), 106 (12), 78 (100), 66 (59), 50 (13), 40 (21); IR: n
3057, 2963, 2914, 2835, 1732, 1568, 1436, 1379, 1295, 1152, 1086, 1051, 1006,
755, 645 cmÀ1; elemental analysis calcd (%) for C13H11NO4 (245.07): C
63.67, H 4.52, N 5.71; found C 63.59, H 4.62, N 5.60.
All other cycloalkynes shown in Table 3were prepared analogously. The
analytical data of new compounds are compiled below. For a full set of the
analytical and spectroscopic data of product 36 see ref. [19], for those of
compounds 4, 22 and 50 see ref. [16] (Supporting Information).
1,7-Dioxa-4-thiacyclotridec-10-yne-2,6-dione (24): M.p. 75 768C; 1H NMR
(CDCl3, 300 MHz): d 4.28 (t, J 5.4 Hz, 4H), 3.43 (s, 4H), 2.49 (t, J
5.5 Hz, 1H); 13C NMR (CDCl3, 75 MHz): d 169.4, 78.1, 62.9, 34.6, 19.6;
MS (EI): m/z (%): 228 (56), 182 (18), 169 (13), 164 (9), 138 (17), 111 (8), 96
(23), 78 (100), 66 (41), 39 (25); IR: n 2963, 2924, 2893, 1756, 1738, 1458,
1417, 1286, 1215, 1146, 1018, 857, 711 cmÀ1; elemental analysis calcd (%) for
C10H12O4S (228.05): C 52.62, H 5.30; found C 52.78, H 5.40.
5,8,10-Trioxacyclotridecyne (26): 1H NMR (CD2Cl2, 300 MHz): d 3.68
3.60 (m, 8H), 3.59 3.53 (m, 4H), 2.36 (t, J 5.5 Hz, 4H); 13C NMR
(CD2Cl2, 75 MHz): d 79.4, 70.3, 69.9, 69.2, 20.8; MS (EI): m/z (%): 184
(<1), 169 (1), 153(2), 139 (14), 125 (7), 109 (76), 96 (46), 79 (69), 66 (100),
52 (18), 45 (75), 40 (44), 28 (25); elemental analysis calcd (%) for C10H16O3
(184.23): C 65.19, H 8.75; found C 65.13, H 8.67.
2-Oxabicyclo[15.3.1]heneicosa-1(21),17,19-triene-15-yne-20-carbaldehyde
(44): 1H NMR (CD2Cl2, 300 MHz): d 10.41 (s, 1H), 7.72 (d, J 8.0 Hz,
1H), 7.07 (d, J 1.1 Hz, 1H), 6.99 (d, J 8.0 Hz, 1H), 4.27 (t, J 7.9 Hz,
2H), 2.51 (t, J 5.7 Hz, 2H), 1.90 1.80 (m, 2H), 1.78 1.30 (m, 18H);
13C NMR (CD2Cl2, 75 MHz): d 189.3, 161.2, 132.0, 128.6, 125.0, 123.4,
116.9, 95.2, 81.3, 68.6, 29.9, 29.6, 28.9, 28.9, 28.6, 28.0, 28.0, 27.5, 27.4, 24.1,
19.7; MS (EI): m/z (%): 312 (100), 283(10), 269 (2), 241 (2), 187 (8), 173(9),
159 (10), 145 (14), 115 (10), 95 (7), 81 (9), 67 (11), 55 (27), 41 (32); IR: n
3074, 2926, 2854, 2229, 1686, 1600, 1559, 1413, 1264, 1177, 1107, 1025, 855,
3,3-Dimethyl-1,5-dioxacycloundec-8-yne-2,4-dione (30a): 1H NMR
(CDCl3, 300 MHz): d 4.31 (t, J 5.8 Hz, 4H), 2.44 (t, J 5.9 Hz, 4H),
1.45 (s, 6H); 13C NMR (CDCl3, 75 MHz): d 172.0, 79.8, 61.8, 50.0, 22.1,
19.7; MS (EI): m/z (%): 210 (<1), 180 (<1), 152 (2), 137 (2), 111 (4), 87 (4),
78 (100), 70 (45), 65 (17), 51 (3), 41 (13); IR: n 2982, 2926, 2850, 1737,
1719, 1464, 1392, 1276, 1171, 1127, 1024, 895, 838 cmÀ1; elemental analysis
calcd (%) for C11H14O4 (210.23): C 62.85, H 6.71; found C 63.01, H, 6.67.
824, 631 cmÀ1
; HR-MS (C21H28O2): calcd 312.2089, found 312.2086;
3,3,14,14-Tetramethyl-2,4,13,15-tetraoxo-1,5,12,16-tetraoxacyclodocosa-
8,19-diyne (30b): 1H NMR (CDCl3, 300 MHz): d 4.12 (t, J 6.8 Hz, 8H),
2.50 (t, J 6.9 Hz, 8H), 1.41 (s, 12H); 13C NMR (CDCl3, 75 MHz): d
172.2, 63.2, 49.1, 29.4, 22.3, 18.5; MS (EI): m/z (%): 420 (5), 342 (1), 306 (1),
219 (1), 174 (8), 156 (51), 141 (14), 115 (6), 96 (8), 78 (100), 69 (30), 41(18);
IR: n 2958, 2928, 2856, 1732, 1463, 1383, 1282, 1265, 1165, 1131, 1026, 892,
elemental analysis calcd (%) for C21H28O2 (312.21): C 80.73, H 9.03; found
C 80.62, H 8.91.
2-Nitro-7,8,9,10,11,12,13,14,15,16,19,20,21,22,23,24,25,26,27,28-eicosahy-
dro-6,29-dioxabenzocyclooctacos-17-yne-5,30-dione (46): M.p. 71 728C;
1H NMR (CD2Cl2, 300 MHz): d 8.60 (d, J 2.2 Hz, 1H), 8.40 (dd, J 2.3,
8.4 Hz, 1H), 7.87 (d, J 8.4 Hz, 1H), 4.33 (dt, J 4.3, 7.0 Hz, 4H), 2.16 (m,
4H), 1.85 1.65 (m, 4H), 1.54 1.22 (m, 28H); 13C NMR (CD2Cl2, 75 MHz):
d 166.6, 165.6, 149.2, 138.7, 133.7, 130.5, 126.2, 124.6, 80.8, 67.0, 30.1, 29.9,
29.9, 29.8, 29.5, 29.3, 29.1, 29.0, 28.9, 28.8, 26.2, 26.2, 18.8; MS (EI): m/z (%):
513 (3), 496 (9), 371 (2), 319 (4), 194 (33), 178 (25), 135 (14), 121 (20), 107
(19), 95 (43), 81 (62), 67 (71), 55 (100), 41 (72); IR: n 3109, 3077, 2920,
2852, 1742, 1724, 1613, 1585, 1534, 1468, 1355, 1304, 1242, 1138, 1062, 963,
934, 835, 734 cmÀ1; HR-MS (C30H43NO6): calcd 513.3090, found 513.3115;
elemental analysis calcd (%) for C30H43NO6 (513.67): C 70.15, H 8.44;
found C 69.96, H 8.41.
1,3-Dioxa-2,2-diphenyl-2-silacyclopentacos-14-yne (48): 1H NMR (CDCl3,
300 MHz): d 7.64 (d, J 7.7 Hz, 4H), 7.42 7.26 (m, 6H), 3.75 (t, J
6.7 Hz, 4H), 2.15 (m, 4H), 1.67 1.18 (m, 32H); 13C NMR (CDCl3,
75 MHz): d 134.9, 133.2, 130.1, 127.8, 80.6, 63.2, 32.5, 29.7, 29.6, 29.4, 29.2,
28.6, 28.4, 25.6, 18.6; MS (EI): m/z (%): 518 (27), 440 (84), 397 (9), 383 (9),
362 (29), 341 (8), 279 (6), 245 (8), 199 (100), 183 (32), 163 (14), 139 (89), 123
(36), 91 (30), 55 (49); elemental analysis calcd (%) for C34H50O2Si (518.85):
C 78.71, H 9.71; found C 78.66, H 9.62.
802 cmÀ1
.
3-Oxabicyclo[14.3.1]eicosa-1(19),16(20),17-trien-14-yne-2-one (32): M.p.
95 968C; 1H NMR (CD2Cl2, 300 MHz): d 8.17 (s, 1H), 7.93(d, J
7.7 Hz, 1H), 7.51 (d, J 7.7 Hz, 1H), 7.40 (t, J 7.8 Hz, 1H), 4.27 (t, J
5.3Hz, 2H), 2.45 (m, 3H), 1.85 1.75 (m, 3H), 1.71 1.31 (m, 12H);
13C NMR (CD2Cl2, 75 MHz): d 166.0, 134.7, 134.0, 131.2, 128.9, 128.5,
124.8, 92.9, 81.0, 66.1, 29.8, 29.3, 29.2, 29.1, 29.0, 27.9, 27.7, 26.9, 19.6; MS
(EI): m/z (%): 284 (100), 214 (8), 200 (12), 186 (29), 170 (20), 155 (28), 142
(47), 129 (58), 115 (42), 91 (14), 81 (53), 67 (46), 55 (54), 41 (44); elemental
analysis calcd (%) for C19H24O2 (284.18): C 80.24, H 8.51; found C 79.88, H,
8.46.
1-(N-Methyl)-azacycloheptadec-12-yne-2-one (34): 1H NMR (CD2Cl2,
300 MHz, rotamers): d 3.41 (t, J 6.8 Hz, 1H), 3.28 (t, J 7.4 Hz, 1H),
2.98 (s, 1H), 2.88 (s, 2H), 2.34 (t, J 6.9 Hz, 2H), 2.26 2.13(m, 4H), 1.80
1.25 (m, 18H); 13C NMR (CD2Cl2, 75 MHz): d 173.0, 172.5, 80.9, 80.8,
80.4, 80.0, 50.1, 46.8, 33.3, 31.3, 28.4, 28.3, 28.2, 28.2, 28.1, 28.0, 27.8, 27.5,
27.1, 27.1, 27.0, 25.3, 24.3, 19.1, 18.9, 18.8; MS (EI): m/z (%): 263(30), 248
(25), 234 (6), 220 (11), 206 (6), 192 (5), 180 (10), 166 (11), 152 (13), 138 (6),
124 (21), 111 (30), 93 (13), 79 (24), 70 (82), 55 (29), 44 (100); IR: n 2926,
Representative procedure for alkyne homodimerization reactions and
alkyne cross metathesis reactions (ACM)
2855, 1647, 1459, 1438, 1401, 1333, 1272, 1170, 1091, 742, 575 cmÀ1
;
elemental analysis calcd (%) for C17H29NO (263.22): C 77.51, H 11.10, N
5.32; found C 77.38, H 11.18, N 5.19.
Preparation of 2-(5-chloro-pent-1-ynyl)-benzoic methyl ester (66): Pro-
pynyl ester 59 (160 mg, 0.91 mmol) and 1,8-dichloro-oct-4-yne (247 mg,
5310
¹ WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2001
0947-6539/01/0724-5310 $ 17.50+.50/0
Chem. Eur. J. 2001, 7, No. 24