P. Xing et al. / Tetrahedron Letters 54 (2013) 699–702
701
Table 2
Hapke, M. Adv. Synth. Catal. 2011, 353, 3423; (c) Sugiyama, Y. K.; Kato, R.;
Sakurada, T.; Okamoto, S. J. Am. Chem. Soc. 2011, 133, 9712; (d) Eichman, C. C.;
Bragdon, J. P.; Stambuli, J. P. Synlett 2011, 1109; (e) Turek, P.; Hocek, M.; Pohl,
R.; Klepetarova, B.; Kotora, M. Eur. J. Org. Chem. 2008, 19, 3335; (f) Hilt, G.;
Hengst, C.; Hess, W. Eur. J. Org. Chem. 2008, 13, 2293; (g) Agenet, N.; Gandon, V.;
Vollhardt, K. P. C.; Malacria, M.; Aubert, C. J. Am. Chem. Soc. 2007, 129, 8860; (h)
Chang, H.-T.; Jeganmohan, M.; Cheng, C.-H. Org. Lett. 2007, 9, 505; (i) Lombardo,
M.; Pasi, F.; Trombini, C.; Seddon, K. R.; Pitner, W. R. Green Chem. 2007, 9, 321;
(j) Hilt, G.; Vogler, T.; Hess, W.; Galbiati, F. Chem. Commun. 2005, 11, 1474; (k)
Hilt, G.; Hess, W.; Vogler, T.; Hengst, C. J. Organomet. Chem. 2005, 690, 5170; (l)
Petit, M.; Aubert, C.; Malacria, M. Org. Lett. 2004, 6, 3937.
The catalytic cycloisomerizationa
Co2(CO)8 (10% mol)
ligand (10% mol)
toluene,relux
t-Bu
2f
t-Bu
1f
Entry
Time (h)
Ligand
Yieldb (%)
3. (a) Shore, N. E. In Comprehensive Organic Synthesis; Trost, B. M., Felming, I.,
Paquette, L. A., Eds.; Pergamon Press: Oxford, 1991; Vol. 5, pp 1037–1064; (b)
Geis, O.; Schmalz, H.-G. Angew. Chem., Int. Ed. 1998, 37, 911; (c) Gibson, S. E.;
Mainolfi, N. Angew. Chem., Int. Ed. 2005, 44, 3022; (d) Cambeiro, X. C.; Pericas,
M. A. In The Pauson–Khand Reaction: Scope, Variations and Applications; Rios
Torres, R., Ed.; John Wiley & Sons, 2012.
4. For reviews see (a) Hilt, G. Synlett 2011, 1654; (b) Lautcns, M.; Tam, W.;
CraigLautens, J.; Edwards, C. G.; Crudden, C. M.; Smith, C. J. Am. Chem. Soc. 1995,
117, 6863; For examples see (c) Arndt, M.; Hilt, G.; Khlebnikov, A. F.;
Kozhushkov, S. I.; Meijere, A. Eur. J. Org. Chem. 2012, 16, 3112; (d) Erver, F.;
Hilt, G. Org. Lett. 2012, 14, 1884; (e) Reus, C.; Liu, N.-W.; Bolte, M.; Lerner, H.-
W.; Wagner, M. J. Org. Chem. 2012, 77, 3518; (f) Erver, F.; Hilt, G.; Harms, K.
Synthesis 2011, 972; (g) Hilt, G.; Arndt, M.; Weske, D. F. Synthesis 2010, 1321;
(h) Hilt, G.; Janikowski, J. Org. Lett. 2009, 11, 773; (i) Moerschel, P.; Janikowski,
J.; Hilt, G.; Frenking, G. J. Am. Chem. Soc. 2008, 130, 8952; (j) Hilt, G.; Danz, M.
Synthesis 2008, 225; (k) Hilt, G.; Hess, W.; Harms, K. Org. Lett. 2006, 8, 3287; (l)
Hilt, G.; Jaikowski, J.; Hess, W. Angew. Chem., Int. Ed. 2006, 45, 5204; (m) Hilt,
G.; Luers, S.; Harms, K. J. Org. Chem. 2004, 69, 624.
1
2
3
16
1.5
1.5
None
Ph3P
rac-BINAP
—
89
>99
O
S
Tol
4
1.5
>99
5
6
1.5
1.5
BuSMe
CyNH2
90
>99
a
Reaction was carried out under argon atmosphere.
Isolated yield.
b
(entry 1). When a ligand such as Ph3P (entry 2), rac-Binap (entry 3),
sulfone (entry 4), sulfide (entry 5), or amine (entry 6) was used, all
the cycloisomerization with 10% mol of Co2(CO)8 completed in
excellent yields (>90%) in only 1.5 h.
5. (a) Hilt, G.; Erver, F.; Harms, K. Org. Lett. 2011, 13, 304; (b) Hilt, G.; Paul, A.;
Treutwein, J. Org. Lett. 2010, 12, 1536; (c) Hilt, G.; Treutwein, J. Angew. Chem.,
Int. Ed. 2007, 46, 8500; (d) Hutson, G. E.; Dave, A. H.; Rawal, V. H. Org. Lett. 2007,
9, 3869; (e) Kezuka, S.; Ikeno, T.; Yamada, T. Org. Lett. 2001, 3, 1937; (f) Llerena,
D.; Aubert, C.; Malacria, M. Tetrahedron Lett. 1996, 37, 7027.
In conclusion, the cycloisomerization of various arylene 1,7-
enynes mediated by Co2(CO)8 has been studied, and high yields
of 2,3-dihydroindene have been achieved. We also demonstrated
a catalytic version of this reaction with 10% mol of Co2(CO)8 and
Lewis base ligands.
6. (a) Buisine, O.; Aubert, C.; Malacria, M. Chem. Eur. J. 2001, 7, 3517; (b) Llerena,
D.; Aubert, C.; Malacria, M. Tetrahedron Lett. 1996, 37, 7353.
7. (a) Ajamian, A.; Gleason, J. L. Org. Lett. 2003, 5, 2409; (b) Ajamian, A.; Gleason, J.
L. Org. Lett. 2001, 3, 4161; (c) Dolaine, R.; Gleason, J. L. Org. Lett. 2000, 2, 1753.
8. (a) Jiang, B.; Xu, M. Angew. Chem., Int. Ed. 2004, 43, 2543; (b) Jiang, B.; Xu, M.
Org. Lett. 2002, 4, 4077.
9. Khand, I. U.; Knox, G. R.; Pauson, P. L.; Watts, W. E. J. Chem. Soc. Chem. Commun.
1971, 1, 36.
10. Magnus, P.; Principe, L. M. Tetrahedron Lett. 1985, 26, 4851.
Acknowledgments
11. Magnus, P.; Exon, C.; Albaugh-Robertson, P. Tetrahedron 1985, 41, 5861.
12. Magnus, P.; Principe, L. M.; Slater, M. J. J. Org. Chem. 1987, 52, 1483.
13. (a) Wellington, K. D.; Cambie, R. C.; Rutledge, P. S.; Bergquist, P. R. J. Nat. Prod.
2000, 63, 79; (b) Madu, C. M.; Lovely, C. J. Org. Lett. 2007, 9, 4697; (c) Arnaiz, E.;
Blanco-Urgoiti, J.; Abdi, D.; Dominguez, G.; Castells, J. P. J. Organomet. Chem.
2008, 693, 2431.
We are grateful for the National Basic Research Program of
China (2010CB833200 and 2010CB833300), the National Natural
Science Foundation of China (20832007 and 21102167), the
Science and Technology Commission of Shanghai Municipality
(12DZ1930902) and the Knowledge Innovation Program of the
Chinese Academy of Sciences.
14. Bonaga, L. V. R.; Krafft, M. E. Tetrahedron 2004, 60, 9795.
15. General procedure for the stoichiometric cycloisomerization of 1a–1i: A mixture of
1,7-enyne 1 (0.1 mmol) and Co2(CO)8 (0.11 mmol) in PhMe (4 mL) was stirred
at room temperature under argon atmosphere for 1 h. Then it was heated to
reflux for 5 h. The resultant reaction mixture was concentrated, the residue
was purified by flash chromatogra-phy on silica gel to provide 2,3-
dihydroindene 2.
Supplementary data
16. (Z)-4-Methoxy-6-methyl-1-(2-methylpropylidene)-2-(prop-1-en-2-yl)-2,3-
dihydro-1H-indene (2a): 1H NMR: d 7.05 (s, 1H), 6.55 (s, 1H), 5.21 (dd, J = 9.4,
1.9 Hz, 1H), 4.82 (s, 1H), 4.77 (s, 1H), 3.83 (s, 3H), 3.62–3.54 (m, 1H), 3.24–3.08
(m, 1H), 2.99 (dd, J = 16.7, 9.1 Hz, 1H), 2.72 (dd, J = 16.7, 5.4 Hz, 1H), 2.38 (s,
3H), 1.59 (s, 3H), 1.08 (t, J = 6.1 Hz, 6H). 13C NMR: d 155.9, 147.9, 140.0, 137.7,
132.6, 130.8, 117.3, 112.0, 109.9, 55.2, 52.8, 32.0, 27.1, 23.1, 23.0, 22.0, 17.9. EI-
MS m/z (%): 256 (M+, 62.72), 213 (100). HRMS (EI) calcd for C18H24O: 256.1827;
Supplementary data associated with this article can be found, in
References and notes
found: 256.1835. IR (KBr): 2959, 1586, 1465, 1287, 890, 830 cmꢀ1
.
1. For reviews see (a) Michelet, V.; Toullec, P. Y.; Genet, J.-P. Angew. Chem., Int. Ed.
2008, 47, 4268; (b) Zhang, L.-M.; Sun, J.-W.; Kozmin, S. A. Adv. Synth. Catal.
2006, 348, 2271; (c) Trost, B. M.; Frederiksen, M. U.; Rudd, M. T. Angew. Chem.,
Int. Ed. 2005, 44, 6630; (d) Solan, G. A. Organomet. Chem. 2005, 32, 314; (e)
Aubert, C.; Buisine, O.; Malacria, M. Chem. Rev. 2002, 102, 813; (f) Trost, B. M.;
Toste, F. D.; Pinkerton, A. B. Chem. Rev. 2001, 101, 2067; (g) Trost, B. M. Chem.
Eur. J. 1998, 4, 2405; (h) Trost, B. M.; Krische, M. J. Synlett 1998, 1; (i) Ojima, I.;
Tzamarioudaki, M.; Li, Z. Y.; Donovan, R. J. Chem. Rev. 1996, 96, 635; For
examples see (j) Gryparis, C.; Efe, C.; Raptis, C.; Lykakis, I. N.; Stratakis, M. Org.
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3674; (o) Lopez-Carrillo, V.; Huguet, N.; Mosquera, A.; Echavarren, A. Chem. Eur.
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Lehmann, C. W. J. Am. Chem. Soc. 1992, 2008, 130; (s) Fuerstner, A.; Martin, R.;
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(Z)-1-(Cyclopropylmethylene)-4-methoxy-6-methyl-2-(prop-1-en-2-yl)-2,3-
dihydro-1H-indene (2b): 1H NMR: d 7.26 (s, 1H), 6.56 (s, 1H), 4.86 (d, J = 9.1 Hz,
1H), 4.77 (d, J = 13.1 Hz, 1H), 3.83 (s, 3H), 3.58 (t, J = 6.3 Hz), 3.00 (dd, J = 16.7,
9.0 Hz, 1H), 2.73 (dd, J = 16.6, 5.3 Hz, 1H), 2.38 (s, 3H), 2.10–1.94 (m, 1H), 1.58
(s, 3H), 0.92–0.83 (m, 2H), 0.48–0.37 (m, 2H). 13C NMR: d 155.8, 147.8, 142.4,
142.0, 137.6, 130.5, 128.1, 117.0, 112.0, 110.0, 55.1, 52.9, 32.0, 22.0, 17.9, 10.8,
7.9, 7.8. EI-MS m/z (%): 254 (M+, 42.97), 199 (100). HRMS (EI) calcd for C18H22O:
254.1671; found: 254.1667. IR (KBr): 2926, 1716, 1595, 1464, 1314,
1139 cmꢀ1
.
(Z)-1-(2,2-Dimethylpropylidene)-4-methoxy-6-methyl-2-(prop-1-en-2-yl)-2,3-
dihydro-1H-indene (2c): 1H NMR: d 7.20 (s, 1H), 6.55 (s, 1H), 5.48 (s, 1H), 4.78
(s, 1H), 4.74 (s, 1H), 3.82 (s, 3H), 3.53 (t, J = 6.6 Hz, 1H), 2.96 (dd, J = 16.6, 9.1 Hz,
1H), 2.68 (dd, J = 16.6, 4.5 Hz, 1H), 2.35 (s, 3H), 1.55 (s, 3H), 1.28 (s, 9H). 13C
NMR: d 155.7, 148.5, 141.5, 140.5, 136.9, 135.9, 132.0, 120.1, 112.0, 109.8, 55.2,
55.1, 31.8, 31.6, 30.5, 22.1, 17.9. EI-MS m/z (%): 270 (M+, 48.82), 213 (100).
HRMS (EI) calcd for C19H26O: 270.1984; found: 270.1984. IR (KBr): 2961, 1646,
1585, 1296, 833 cmꢀ1
.
(Z)-1-Benzylidene-4-methoxy-6-methyl-2-(prop-1-en-2-yl)-2,3-dihydro-1H-
indene (2d): 1H NMR: d 7.42–7.26 (m, 4H), 6.64 (s, 1H), 6.50 (s, 1H), 6.44 (s, 1H),
4.93 (s, 1H), 4.85 (s, 1H), 3.81 (s, 3H), 3.80–3.71 (m, 1H), 3.07 (dd, J = 16.7,
9.1 Hz, 1H), 2.80 (dd, J = 16.7, 5.4 Hz, 1H), 2.14 (s, 3H), 1.67 (s, 3H). 13C NMR: d
155.9, 147.5, 145.0, 141.1, 138.4, 137.2, 131.9, 128.6, 128.2, 126.7, 123.1, 117.2,
2. For reviews see (a) Dominguez, G.; Perez-Castells, J. Chem. Soc. Rev. 2011, 40,
3430; For examples see (b) Weding, N.; Jackstell, R.; Jiao, H.; Spannenberg, A.;