LETTER
Cobalt Carbonyl-Catalyzed Tandem [2+2+1]/[4+2] Cycloaddition of Dienediyne
1891
In conclusion, a cobalt carbonyl-catalyzed tandem
2+2+1]/[4+2] cycloaddition reaction of dienediyne has
been developed, yielding new tetracycles. Further studies
on the application of the new tetracycles as molecular
scaffolds are underway.
(CDCl
9.9, 69.0, 57.4, 27.5, 18.2, 17.8, 17.6. HRMS: m/z calcd for
C H O : 202.1358; found: 202.1353.
3
): d = 134.0, 130.8, 130.3, 126.0, 85.6, 83.5, 76.8,
6
[
1
4
18
1
1
Compound 2d: yield 63%. H NMR (CDCl ): d = 6.23 (dd,
3
J = 10.4, 15.1 Hz, 1 H), 6.06 (dd, 10.6, 14.8 Hz, 1 H), 5.73
(
m, 1 H), 5.61 (m, 1 H), 4.13 (t, J = 1.9 Hz, 2 H), 4.07 (d,
J = 6.4 Hz, 2 H), 3.38–3.34 (m, 4 H), 3.35 (s, 3 H), 3.34 (s,
H), 2.39 (t, J = 1.9 Hz, 2 H), 2.33 (d, J = 2.6 Hz, 2 H), 1.98
3
1
3
(
(
t, J = 2.6 Hz, 1 H), 1.76 (d, J = 6.6 Hz, 3 H). C NMR
CDCl ): d = 134.0, 130.7, 130.3, 125.9, 83.0, 80.8, 78.2,
General Procedure for [2+2+2] Cycloaddition
3
To a 100-mL high-pressure reactor were added 6d (0.20 g, 0.71
mmol), 30 mL of CH Cl , and Co (CO) (12 mg, 36 mmol). After the
73.6, 70.4, 69.7, 59.4, 57.3, 41.8, 22.2, 21.9, 18.1. HRMS:
2
2
2
8
m/z calcd for C H O : 290.1882; found: 290.1883.
1
8
26
3
solution was flushed with CO gas in several seconds, the reactor
was pressurized with 30 atm of CO. The reactor was heated at 130
1
Compound 3d: yield 71%. H NMR (CDCl ): d = 6.22 (dd,
3
J = 10.4, 15.0 Hz, 1 H), 6.06 (m, 1 H), 5.74 (m, 1 H), 5.60
°C for 18 h. After the reactor was cooled to r.t. and excess gas was
(
m, 1 H), 4.31 (t, J = 1.7 Hz, 2 H), 4.25 (s, 2 H), 4.18 (t,
relieved, the solution was transferred into a flask and then evaporat-
ed to dryness. The residue was chromatographed on a silica gel col-
umn eluting with hexane and EtOAc (v/v, 10:1).
J = 1.7 Hz, 2 H), 4.06 (d, J = 6.4 Hz, 2 H), 2.45 (m, 1 H),
1
3
1
1
5
2
.75 (d, J = 6.7 Hz, 3 H). C NMR (CDCl ): d = 134.3,
3
30.8, 130.6, 125.7, 83.3, 81.4, 79.0, 75.1, 70.2, 57.1, 56.9,
6.5, 18.2. HRMS: m/z calcd for C H O : 204.1150; found:
1
3
16
2
04.1155.
Acknowledgment
1
Compound 4d: yield 83%. H NMR (CDCl ): d = 6.23 (dd,
3
This work is supported by grant No. [R02-2004-000-10005-
J = 10.5, 14.9 Hz, 1 H), 6.06 (m, 1 H), 5.74 (m, 1 H), 5.60
0
(2004)] from the Basic Research Program of the Korea Science &
(
(
1
m, 1 H), 4.28 (t, J = 1.7 Hz, 2 H), 4.22–4.18 (m, 2 H), 4.17
Engineering Foundation. Authors thank Dr. Son for his initial study
of this project. DHK acknowledges receipt of the BK21 fellowship.
d, J = 1.7 Hz, 2 H), 4.06 (d, J = 6.4 Hz, 2 H), 1.86 (m, 3 H),
13
.76 (d, J = 6.4 Hz, 3 H). C NMR (CDCl ): d = 134.2,
3
130.8, 130.5, 125.7, 83.2, 82.8, 81.8, 74.4, 70.1, 57.2, 57.1,
5
6.6, 18.2, 3.6. HRMS: m/z calcd for C H O : 218.1307;
1
4
18
2
References
found: 218.1309.
Compound 5d: yield 77%. H NMR (CDCl ): d = 6.23 (dd,
J = 10.5, 15.0 Hz, 1 H), 6.07 (dd, J = 10.5, 15.0 Hz, 1 H),
1
(
1) For recent reviews, see: (a) Carreno, M. C.; Urbano, A.
Synlett 2005, 1. (b) Rodríguez Rivero, M.; Adrio, J.;
Carretero, J. C. Synlett 2005, 26. (c) France, S.;
3
5.73 (m, 1 H), 5.61 (m, 1 H), 4.29 (s, 2 H), 4.23 (t, J = 1.7
Hz, 2 H), 4.18 (s, 2 H), 4.07 (d, J = 6.4 Hz, 2 H), 2.23 (t,
J = 6.8 Hz, 2 H), 1.76 (d, J = 6.6 Hz, 3 H), 1.47 (m, 2 H),
Weatherwax, A.; Taggi, A. E.; Lectka, T. Acc. Chem. Res.
2004, 37, 592. (d) Harvey, R. G. Curr. Org. Chem. 2004, 8,
303. (e) Denissova, I.; Barriault, L. Tetrahedron 2003, 59,
10105.
1
3
1
.42 (m, 2 H), 0.91 (t, J = 7.2 Hz, 3 H). C NMR (CDCl3):
d = 134.4, 130.8, 130.7, 125.8, 82.9, 81.9, 75.1, 70.2, 57.4,
7.2, 56.7, 31.8, 30.8, 22.1, 18.6, 18.3, 13.8. HRMS: m/z
calcd for C H O : 260.1776; found: 260.1776.
5
(
2) For recent reviews, see: (a) Bolm, C.; Legros, J.; Le Paih, J.;
Zani, L. Chem. Rev. 2004, 104, 6217. (b) Montgomery, J.
Angew. Chem. Int. Ed. 2004, 43, 3890. (c) Zeni, G.; Larock,
R. C. Chem. Rev. 2004, 104, 2285. (d) Nakamura, I.;
Yamamoto, Y. Chem. Rev. 2004, 104, 2127. (e) Varela, J.
A.; Saa, C. Chem. Rev. 2003, 103, 3787.
17 24
2
1
Compound 6d: yield 66%. H NMR (CDCl ): d = 7.47–7.44
3
(
m, 2 H), 7.33–7.30 (m, 3 H), 6.23 (dd, J = 10.4, 15.0 Hz, 1
H), 6.06 (m, 1 H), 5.73 (m, 1 H), 5.61 (m, 1 H), 4.48 (s, 2 H),
.38 (t, J = 1.7 Hz, 2 H), 4.20 (t, J = 1.7 Hz, 2 H), 4.08 (d,
4
1
3
J = 6.5 Hz, 2 H), 1.75 (d, J = 6.8 Hz, 3 H). C NMR
CDCl ): d = 134.2, 131.8, 130.6, 130.5, 128.5, 128.3, 125.6,
(3) (a) Ajamian, A.; Gleason, L. Angew. Chem. Int. Ed. 2004,
(
43, 3754. (b) Lee, J. M.; Na, Y.; Han, H.; Chang, S. Chem.
3
122.4, 86.8, 84.2, 83.1, 81.5, 70.1, 57.3, 57.1, 56.9, 18.1.
Soc. Rev. 2004, 33, 302. (c) Fogg, D. E.; dos Santos, E. N.
Coord. Chem. Rev. 2004, 248, 2365. (d) Wasilke, J.-C.;
Obrey, S. J.; Baker, R. T.; Bazan, G. C. Chem. Rev. 2005,
HRMS: m/z calcd for C H O : 280.1463; found: 280.1469.
Compound 7d: yield 65%. H NMR (CDCl ): d = 7.42–7.30
19 20
1
2
3
(
m, 4 H), 7.30–7.09 (m, 6 H), 6.71 (dd, J = 10.5, 15.6 Hz, 1
105, in press. (e) Ramon, D. J.; Yus, M. Angew. Chem. Int.
H), 6.48 (d, J = 15.6 Hz, 1 H), 5.37 (dd, J = 10.5, 15.2 Hz, 1
H), 5.79 (dt, J = 6.3, 15.2 Hz, 1 H), 4.42 (s, 2 H), 4.31 (t,
J = 1.7 Hz, 2 H), 4.16 (t, J = 1.7 Hz, 2 H), 4.09 (d, J = 6.3
Ed. 2005, 44, 1602.
(
4) Wender, P. A.; Gamber, G.; Hubbard, R. D.; Pham, S. M.;
Zhang, L. J. Am. Chem. Soc. 2005, in press; and references
therein.
1
3
Hz, 2 H). C NMR (CDCl ): d = 137.2, 134.0, 133.3, 131.9,
3
129.1, 128.8, 128.7, 128.5, 128.2, 127.8, 126.6, 122.6, 87.0,
(
(
5) Kim, D. H.; Chung, Y. K. Chem. Commun. 2005, 1634.
6) (a) Son, S. U.; Park, K. H.; Lee, S. J.; Kim, B. M.; Chung, Y.
K. Synlett 2003, 1101. (b) Kim, D. H.; Son, S. U.; Chung, Y.
K.; Lee, S.-G. Chem. Commun. 2002, 56. (c) Son, S. U.;
Yoon, Y. A.; Choi, D. S.; Park, J. K.; Kim, B. M. Org. Lett.
84.3, 83.1, 81.9, 70.1, 57.5, 57.4, 57.0. HRMS: m/z calcd for
C H O : 342.1620; found: 342.1613.
Compound 8d: yield 70%. H NMR (CDCl ): d = 7.57 (d,
J = 8.2 Hz, 2 H), 7.27–7.25 (m, 2 H), 7.17–7.09 (m, 3 H),
24 22
2
1
3
7
5
3
3
1
.13 (d, J = 8.2 Hz, 2 H), 5.99 (dd, J = 10.4, 15.0 Hz, 1 H),
.84 (m, 1 H), 5.54 (m, 1 H), 5.25 (m, 1 H), 4.08 (s, 2 H),
.96 (s, 2 H), 3.90 (s, 2 H), 3.66 (d, J = 6.9 Hz, 2 H), 2.22 (s,
2001, 3, 1065. (d) Son, S. U.; Chung, Y. K.; Lee, S. G. J.
Org. Chem. 2000, 65, 6142. (e) Son, S. U.; Choi, D. S.;
Chung, Y. K. Org. Lett. 2000, 2, 2097. (f) Hong, S. H.;
Choi, D. S.; Chung, Y. K.; Lee, S. Chem. Commun. 1999,
1
3
H), 1.57 (d, J = 6.6 Hz, 3 H). C NMR (CDCl ): d = 143.7,
3
36.3, 135.7, 131.9, 131.2, 130.5, 129.7, 128.9, 128.6,
2099.
1
128.0, 123.6, 122.6, 87.0, 84.2, 81.0, 80.0, 57.3, 56.7, 48.7,
(
7) Compound 1d: yield 59%. H NMR (CDCl ): d = 6.22 (dd,
3
36.2, 21.7, 18.2. HRMS: m/z calcd for C H O N S :
J = 10.4, 15.1 Hz, 1 H), 6.06 (dd, 10.6, 14.9 Hz, 1 H), 5.70
26 27 3 1 1
433.1712; found: 433.1715.
(
m, 1 H), 5.54 (m, 1 H), 4.10 (t, J = 2.1 Hz, 2 H), 4.04 (d,
1
Compound 1: yield 23%. H NMR (CDCl ): d = 6.07 (dt,
J = 3.3, 8.8 Hz, 1 H), 5.80 (s, 1 H), 5.48 (dt, J = 3.0, 8.8 Hz,
1 H), 4.49 (dd, J = 7.0, 11.4 Hz, 1 H), 4.20 (dd, J = 7.1, 9.0
J = 6.4 Hz, 2 H), 2.36 (tt, J = 2.1, 7.0 Hz, 2 H), 2.30 (dd,
J = 2.6, 7.0 Hz, 2 H), 1.97 (t, J = 2.6 Hz, 1 H), 1.75 (d,
J = 6.6 Hz, 2 H), 1.73 (t, J = 7.0 Hz, 3 H). C NMR
3
1
3
Synlett 2005, No. 12, 1889–1892 © Thieme Stuttgart · New York