E. Duñach et al.
FULL PAPER
Eom, J. Org. Chem. 2006, 71, 6705–6707; e) R.-V. Nguyen, X.
Yao, C.-J. Li, Org. Lett. 2006, 8, 2397–2399; f) L. A. Adrio,
K. K. Hii, Chem. Commun. 2008, 2325–2327; g) A. Malkov,
P. Kocovsky, Collect. Czech. Chem. Commun. 2001, 66, 1257–
1268.
Y. Ishino, M. Mihara, N. Hayakawa, T. Miyata, Y. Kaneko, T.
Miyata, Synth. Commun. 2001, 31, 439–448.
[21] P. Nava, Y. Carissan, S. Humbel, Phys. Chem. Chem. Phys.
2009, 11, 7130–7136.
[22] a) F. Weigend, R. Ahlrichs, Phys. Chem. Chem. Phys. 2005, 7,
3297–3305; b) F. Weigend, Phys. Chem. Chem. Phys. 2006, 8,
1057–1065; c) B. Metz, H. Stoll, M. Dolg, J. Chem. Phys. 2000,
113, 2563–2569.
[11]
[23] Diffuse functions were added to Cl and O atoms with ex-
ponents as in ref.[20]
[12]
[13]
S. W. Youn, Synlett 2007, 3050–3054.
[24] a) A. D. Becke, Phys. Rev. A 1988, 38, 3098–3100; b) J. P. Per-
dew, Phys. Rev. B 1986, 33, 8822–8824.
[25] a) S. H. Vosko, L. Wilk, M. Nusair, Can. J. Phys. 1980, 58,
1200–1211; b) C. Lee, W. Yang, R. G. Parr, Phys. Rev. B 1988,
37, 785–789; c) A. D. Becke, J. Chem. Phys. 1993, 98, 5648–
5652.
[26] a) R. Ahlrichs, M. Baer, M. Haeser, H. Horn, C. Koelmel,
Chem. Phys. Lett. 1989, 162, 165–169; b) O. Treutler, R.
Ahlrichs, J. Chem. Phys. 1995, 102, 346–354; c) K. Eichkorn,
O. Treutler, H. Oehm, M. Haeser, R. Ahlrichs, Chem. Phys.
Lett. 1995, 242, 652–660; d) P. Deglmann, K. May, F. Furche,
R. Ahlrichs, Chem. Phys. Lett. 2004, 384, 103–107; e) P.
Deglmann, F. Furche, R. Ahlrichs, Chem. Phys. Lett. 2002,
362, 511–518.
a) W. Bonrath, Y. Foricher, T. Netscher, A. Wildermann (DSM
IP Assets B. V.), WO 2005054223, 2005; b) W. Bonrath, L. Gi-
raudi (DSM IP Assets B. V.), WO 2005005407, 2005; c) W.
Bonrath, C. Dittel, T. Netscher, T. Pabst, L. Giraudi (DSM IP
Assets B. V.), WO 2004063182, 2004.
J. Ricci, S. Poulain-Martini, E. Duñach, C. R. Acad. Sci. II C
2009, 12, 916–921.
[14]
[15]
For examples of vitamin E synthesis under stoichiometric con-
ditions, see ref.[6c,7b,8a,9a–9d]
[16] For examples of vitamin E synthesis under catalytic conditions,
see: a) T. Ichikawa, T. Kato, Bull. Chem. Soc. Jpn. 1968, 41,
1224–1228; b) M. Matsui, H. Yamamoto, Bull. Chem. Soc. Jpn.
1995, 68, 2663–2668; c) H. Bienayme, J. E. Ancel, P. Meilland,
J. P. Simonato, Tetrahedron Lett. 2000, 41, 3339–3343; d) L.
Tietze, K. Sommer, J. Zinngrebe, F. Stecker, Angew. Chem. Int.
[27] A. E. Reed, R. B. Weinstock, F. Weinhold, J. Chem. Phys. 1985,
83, 735–746.
Ed. 2005, 44, 257–259; e) M. Matsui, N. Karibe, K. Hayashi, [28] In the calculation, the π–allyl corresponds to TS A situated at
H. Yamamoto, Bull. Chem. Soc. Jpn. 1995, 68, 3569–3571; f)
L. Giraudi, W. Bonrath (DSM IP Assets B. V.), US
2005038269, 2005.
–6.1 kcal/mol (Figure 3); its structure is displayed in Figure 4.
[29] M. Fatope, D. Abraham, J. Med. Chem. 1987, 30, 1973–1977.
[30] K. C. Dewhirst, F. F. Rust, J. Org. Chem. 1963, 28, 798–802.
[31] K. Hata, H. Hamamoto, Y. Shiozaki, S. Caemmerer, Y. Kita,
Tetrahedron 2007, 63, 4052–4060.
[32] R. Cichewicz, V. Kenyon, S. Whitman, N. Morales, J. Arguello,
T. Holman, P. Crews, J. Am. Chem. Soc. 2004, 126, 14910–
14920.
[17] a) W. Dauben, J. Cogen, V. Behar, Tetrahedron Lett. 1990, 31,
3241–3244; b) T. Ollevier, T. Mwene-Mbeja, Synthesis 2006,
3963–3966; c) A. Bernard, M. Cocco, V. Onnis, P. Pier, Synthe-
sis 1998, 256–258.
[18] a) L. Harwood, J. Chem. Soc., Chem. Commun. 1983, 530–532;
b) F. Zulfiqar, T. Kitazume, Green Chem. 2000, 2, 296–297; c)
V. Grant, B. Liu, Tetrahedron Lett. 2005, 46, 1237–1239; d) Y.
Ito, R. Kato, K. Hamashima, Y. Kataoka, Y. Oe, T. Ohta, I.
[33] Y. Wang, J. Wu, P. Xia, Synth. Commun. 2006, 36, 2685–2698.
[34] M. Teng, T. Duong, A. Johnson, E. Klein, L. Wang, B. Khal-
ifa, R. Chandraratna, J. Med. Chem. 1997, 40, 2445–2451.
Furukawa, J. Organomet. Chem. 2007, 692, 691–697; e) N. [35] M. Matsuo, S. Urano, Tetrahedron 1976, 32, 229–231.
Reich, C. G. Yang, Z. Shi, C. He, Synlett 2006, 1278–1280; f)
K. Kim, H. Kim, E. Ryu, Heterocycles 1993, 36, 497–505.
[19] S. Gester, P. Metz, O. Zierau, G. Vollmer, Tetrahedron 2001, 57,
1015–1018.
[36] M. Lafrance, S. Gorelsky, K. Fagnou, J. Am. Chem. Soc. 2007,
129, 14570–14571.
[37] L. Tietze, F. Stecker, J. Zinngrebe, K. Sommer, Chem. Eur. J.
2006, 12, 8770–8776.
[20] A. Broom, D. Bartholomew, J. Org. Chem. 1976, 41, 3027–
Received: May 21, 2010
Published Online: September 28, 2010
3030.
6248
www.eurjoc.org
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2010, 6239–6248