A. Wolan et al. / Tetrahedron 65 (2009) 7429–7439
7439
586 m
L) in Et2O (10 mL) at 20 ꢁC. cyclo-Pentylmagnesium chloride
129, 15112–15113; (r) Perez, L. J.; Micalizio, G. C. Synthesis 2008, 627–648; (s)
Shimp, H. L.; Hare, A.; McLaughlin, M.; Micalizio, G. C. Tetrahedron 2008, 64,
3437–3445.
5. Kasatkin, A.; Okamoto, S.; Sato, F. Tetrahedron Lett. 1995, 36, 6075–6078.
6. Okamoto, S.; Kasatkin, A.; Zubaidha, P. K.; Sato, F. J. Am. Chem. Soc. 1996, 118,
2208–2216.
(1.91 M in Et2O, 1.50 equiv, 6.00 mmol, 3.14 mL) was then added
dropwise at 0 ꢁC while carbon dioxide was bubbled into the solu-
tion. After 15 min of stirring at 0 ꢁC, 1 N HCl aq solution (40 mL) and
Et2O (30 mL) were added. The organic layer was separated, and the
aqueous layer extracted with Et2O (2ꢂ40 mL). The combined or-
ganic phases were then dried over MgSO4, filtered and concen-
trated to afford a brown-orange oil (476 mg) that was purified by
flash column chromatography (AcOEt/heptane, gradient from 0% to
2%) afforded compound 16a contaminated with grease (111 mg),
7. (a) Six, Y. J. Chem. Soc., Perkin Trans. 1 2002, 1159–1160; (b) Six, Y. Eur. J. Org.
Chem. 2003, 1157–1171.
8. See also the following selected references: (a) Kolomnikov, I. S.; Lobeeva, T.
S.; Gorbachevskaya, V. V.; Aleksandrov, G. G.; Struckhov, Y. T.; Vol’pin, M. E.
J. Chem. Soc. D, Chem. Commun. 1971, 972–973; (b) Demerseman, B.; Mahe´, R.;
Dixneuf, P. H. J. Chem. Soc., Chem. Commun. 1984, 1394–1396; (c) Shur, V. B.;
Burlakov, V. V.; Yanovskii, A. I.; Struchkov, Y. T.; Vol’pin, M. E. Metalloorg. Khim.
1988, 1, 475; Organomet. Chem. USSR 1988, 1, 261–262; (d) Lefeber, C.; Ohff, A.;
Tillack, A.; Baumann, W.; Kempe, R.; Burlakov, V. V.; Rosenthal, U.; Go¨rls, H.
J. Organomet. Chem. 1995, 501, 179–188; (e) Burlakov, V. V.; Yanovsky, A. I.;
Struchkov, Y. T.; Rosenthal, U.; Spannenberg, A.; Kempe, R.; Ellert, O. G.; Shur,
V. B. J. Organomet. Chem. 1997, 542, 105–112; (f) Thomas, D.; Peulecke, N.;
Burlakov, V. V.; Baumann, W.; Spannenberg, A.; Kempe, R.; Rosenthal, U. Eur. J.
Inorg. Chem. 1998, 1495–1502; (g) Rosenthal, U.; Burlakov, V. V. In Titanium and
Zirconium in Organic Synthesis; Marek, I., Ed.; Wiley-VCH: Weinheim, 2002;
pp 355–389.
pure 15a (70.3 mg, 450
mmol, 11%), and an 85:15 mixture of cyclo-
pentanecarboxylic acid and 15a (43.5 mg, 307 and 54.1
mmol, re-
spectively). The yield of 16a was estimated at 12% by comparing the
integrals of the signals of the ArCH2 protons (2.47 ppm) with that of
the vinylic CH proton of 15a.
4.7.1. (E)-2-Propylhex-2-enoic acid (15a)
9. Takahashi, T.; Xi, C.; Ura, Y.; Nakajima, K. J. Am. Chem. Soc. 2000, 122, 3228–3229.
10. Yamashita, K.; Chatani, N. Synlett 2005, 919–922.
This compound has already been described.7b,39
11. Recent review: Mori, M. Eur. J. Org. Chem. 2007, 4981–4993.
12. Cadoret, F.; Six, Y. Tetrahedron Lett. 2007, 48, 5491–5495.
13. Under these conditions, 1 equiv of 1 is presumably formed, along with 1 equiv
of cyclo-pentyltris(iso-propyloxy)titanium. Cadoret, F.; Retailleau, P.; Six, Y.
Tetrahedron Lett. 2006, 47, 7749–7753.
4.7.2. 1,2,3,4,5,6-Hexapropylbenzene (16a)
This compound has already been described.40
Acknowledgements
14. Eisch, J. J.; Adeosun, A. A.; Gitua, J. N. Eur. J. Org. Chem. 2003, 4721–4727.
´
15. Garnier, J.-M.; Lecornue, F.; Charnay-Pouget, F.; Ollivier, J. Synlett 2007, 2827–
2828.
We are grateful to the Centre National de la Recherche Scientifique
16. Frongia, A.; Girard, C.; Ollivier, J.; Piras, P. P.; Secci, F. Synlett 2008, 2823–2825.
17. Madelaine, C.; Ouhamou, N.; Chiaroni, A.; Vedrenne, E.; Grimaud, L.; Six, Y.
Tetrahedron 2008, 64, 8878–8898.
`
´ ´ ´ `
(CNRS) for financial support, and to the Ministere delegue a l’En-
´
`
seignement superieur et a la Recherche for the funding granted to F.C.
We also warmly thank the people of the analytical services of our
institute.
ˆ
´
18. We warmly thank Dr Mouad Alami (Laboratoire BioCIS-CNRS, Faculte de
Pharmacie, Universite´ Paris-Sud 11, Chaˆtenay-Malabry, France) for a gift of this
compound.
19. (a) Liron, F.; Le Garrec, P.; Alami, M. Synlett 1999, 246–248; (b) Alami, M.; Liron,
F.; Gervais, M.; Peyrat, J.-F.; Brion, J.-D. Angew. Chem., Int. Ed. 2002, 41, 1578–
1580; (c) Hamze, A.; Provot, O.; Alami, M.; Brion, J.-D. Org. Lett. 2005, 7, 5625–
5628; (d) Hamze, A.; Provot, O.; Brion, J.-D.; Alami, M. Synthesis 2007, 2025–2036.
20. It is worthy of note that a similar result has been obtained from the same alkyne
2e in an attempted Ti-mediated carboxylation with carbon dioxide. See Ref. 7.
21. When 3j is treated with Ti(Oi-Pr)4/c-C5H9MgCl at low temperature (ꢀ70 ꢁC to
Supplementary data
Supplementary data associated with this article can be found in
0
ꢁC) in Et2O in the absence of diethyl carbonate, lactam 9 is formed in 26% yield,
along with (Z)-alkene 8j (41% yield). Maka, J. L.; Six, Y., unpublished results.
22. Yamaguchi, S.; Jin, R.-Z.; Tamao, K.; Sato, F. J. Org. Chem. 1998, 63, 10060–10062.
23. The group of Micalizio has reported numerous cases of regioselectivities being
induced by this type of effect. See Ref. 4r, and references cited therein.
24. The Grignard reagent was added dropwise while carbon dioxide was being
bubbled through the reaction mixture!
25. Meijer-Veldman, M. E. E.; de Liefde Meijer, H. J. J. Organomet. Chem. 1984, 260,
199–205.
26. Hill, J. E.; Balaich, G.; Fanwick, P. E.; Rothwell, I. P. Organometallics 1993, 12,
2911–2924.
27. Ozerov, O. V.; Ladipo, F. T.; Patrick, B. O. J. Am. Chem. Soc. 1999, 121, 7941–7942.
28. Eisch, J. J.; Gitua, J. N.; Otieno, P. O.; Shi, X. J. Organomet. Chem. 2001, 624, 229–238.
29. Recent reviews about alkyne cyclotrimerisation reactions: (a) Kotha, S.; Brah-
machary, E.; Lahiri, K. Eur. J. Org. Chem. 2005, 4741–4767; (b) Chopade, P. R.;
Louie, J. Adv. Synth. Catal. 2006, 348, 2307–2327; (c) Agenet, N.; Buisine, O.;
Slowinski, F.; Gandon, V.; Aubert, C.; Malacria, M. In Organic Reaction; Overman,
L. E., Ed.–in–Chief; John Wiley & Sons: Hoboken, 2007; 68, pp 1–302; (d) Galan,
B. R.; Rovis, T. Angew. Chem., Int. Ed. 2009, 48, 2830–2834.
30. Castells, J.; Lo´ pez-Calahorra, F.; Yu, Z. Tetrahedron 1994, 50, 13765–13774.
31. Bellucci, G.; Chiappe, C.; Cordoni, A. Tetrahedron: Asymmetry 1996, 7, 197–202.
32. Takeuchi, R.; Sugiura, M.; Ishii, N.; Sato, N. J. Chem. Soc., Chem. Commun. 1992,
1358–1359.
References and notes
1. Kulinkovich, O. G.; Sviridov, S. V.; Vasilevskii, D. A.; Pritytskaya, T. S. Zh. Org.
Khim. 1989, 25, 2244–2245; Russ. J. Org. Chem. 1989, 25, 2027–2028.
2. Selected reviews: (a) Kulinkovich, O. G.; de Meijere, A. Chem. Rev. 2000, 100,
2789–2834; (b) Sato, F.; Urabe, H.; Okamoto, S. Chem. Rev. 2000, 100, 2835–
2886; (c) Sato, F.; Urabe, H. In Titanium and Zirconium in Organic Synthesis;
Marek, I., Ed.; Wiley-VCH: Weinheim, 2002; pp 319–354; (d) de Meijere, A.;
Kozhushkov, S. I.; Savchenko, A. I. In Titanium and Zirconium in Organic Syn-
thesis; Marek, I., Ed.; Wiley-VCH: Weinheim, 2002; pp 390–434; (e) Kulinko-
vich, O. G. Izv. Akad. Nauk, Ser. Khim. 2004, 1022–1043; Russ. Chem. Bull., Int. Ed.
2004, 53, 1065–1086; (f) de Meijere, A.; Kozhushkov, S. I.; Savchenko, A. I.
J. Organomet. Chem. 2004, 689, 2033–2055; (g) Bertus, P.; Szymoniak, J.
Synlett 2007, 1346–1356.
3. Harada, K.; Urabe, H.; Sato, F. Tetrahedron Lett. 1995, 36, 3203–3206.
4. Selected papers: (a) Gao, Y.; Harada, K.; Sato, F. Tetrahedron Lett. 1995, 36, 5913–
5916; (b) Urabe, H.; Hamada, T.; Sato, F. J. Am. Chem. Soc. 1999, 121, 2931–2932;
(c) Suzuki, D.; Urabe, H.; Sato, F. Angew. Chem., Int. Ed. 2000, 39, 3290–3292; (d)
Okamoto, S.; Subburaj, K.; Sato, F. J. Am. Chem. Soc. 2000, 122, 11244–11245; (e)
Okamoto, S.; Matsuda, S.-I.; An, D. K.; Sato, F. Tetrahedron Lett. 2001, 42, 6323–
6326; (f) Tanaka, R.; Nakano, Y.; Suzuki, D.; Urabe, H.; Sato, F. J. Am. Chem. Soc.
2002, 124, 9682–9683; (g) Nakano, Y.; Ishizuka, K.; Muraoka, K.; Ohtani, H.;
Takayama, Y.; Sato, F. Org. Lett. 2004, 6, 2373–2376; (h) Suzuki, D.; Nobe, Y.;
Watai, Y.; Tanaka, R.; Takayama, Y.; Sato, F.; Urabe, H. J. Am. Chem. Soc. 2005, 127,
7474–7479; (i) Tanaka, R.; Yuza, A.; Watai, Y.; Suzuki, D.; Takayama, Y.; Sato, F.;
Urabe, H. J. Am. Chem. Soc. 2005, 127, 7774–7780; (j) Hirano, S.; Fukudome, Y.;
Tanaka, R.; Sato, F.; Urabe, H. Tetrahedron 2006, 62, 3896–3916; (k) Hungerford,
N. L.; Kitching, W. J. Chem. Soc., Perkin Trans. 11998, 1839–1858; (l) Me´zailles, N.;
Avarvari, N.; Bourissou, D.; Mathey, F.; Le Floch, P. Organometallics 1998, 17,
2677–2679; (m) Baum, O.; Quntar, A. A. A.; Dembitsky, V. M.; Srebnik, M.
Tetrahedron 2004, 60, 1359–1364; (n) Ryan, J.; Micalizio, G. C. J. Am. Chem. Soc.
2006, 128, 2764–2765; (o) Reichard, H. A.; Micalizio, G. C. Angew. Chem., Int. Ed.
2007, 46, 1440–1443; (p) Belardi, J. K.; Micalizio, G. C. Angew. Chem., Int. Ed.
2008, 47, 4005–4008; (q) Kolundzic, F.; Micalizio, G. C. J. Am. Chem. Soc. 2007,
33. Miyata, O.; Fujiwara, Y.; Ninomiya, I.; Naito, T. J. Chem. Soc., Perkin Trans. 1 1998,
2167–2174.
34. Azzena, F.; Calvani, F.; Crotti, P.; Gardelli, C.; Macchia, F.; Pineschi, M. Tetrahe-
dron 1995, 51, 10601–10626.
35. Alonso, F.; Osante, I.; Yus, M. Tetrahedron 2007, 63, 93–102.
36. Myrboh, B.; Ila, H.; Junjappa, H. J. Org. Chem. 1983, 48, 5327–5332.
37. Kobayashi, K.; Ueno, M.; Naka, H.; Kondo, Y. Chem. Commun. 2008, 3780–3782,
Supplementary data.
´
38. Coperet, C.; Sugihara, T.; Wu, G.; Shimoyama, I.; Negishi, E. J. Am. Chem. Soc.
1995, 117, 3422–3431.
39. Brittelli, D. R. J. Org. Chem. 1981, 46, 2514–2520.
40. Li, J.; Jiang, H.; Chen, M. J. Org. Chem. 2001, 66, 3627–3629.