S.-I. Murahashi et al. / Tetrahedron Letters 51 (2010) 2339–2341
2341
Grant-in-Aid for Scientific Research from the Ministry of Education,
Culture, Sports, Science, and Technology of Japan.
O
CH3
CH3
+
HO
CH3
References and notes
CH3
3
11
O
1. (a) Murahashi, S.-I. Angew. Chem., Int. Ed. Engl. 1995, 34, 2443–2465; (b)
Murahashi, S.-I.; Komiya, N. In Biomimetic Oxidations Catalyzed by Transition
Metal Complexes; Meunier, B., Ed.; Imperial College Press: London, 2000; pp
563–611; (c) Murahashi, S.-I.; Komiya, N. In Modern Oxidation Methods;
Bäckvall, J.-E., Ed.; Wiley-VCH: Weinheim, 2004; pp 165–191; (d) Murahashi,
S.-I.; Komiya, N. In Ruthenium in Organic Synthesis; Murahashi, S.-I., Ed.; Wiley-
VCH: Weinheim, 2004; pp 53–93; (e) Murahashi, S.-I.; Zhang, D. Chem. Soc. Rev.
2008, 37, 1490–1501; (f) Piera, J.; Bäckvall, J.-E. Angew. Chem., Int. Ed. 2008, 47,
3506.
2. Sheldon, R. A.; Kochi, J. K. Metal-Catalyzed Oxidations of Organic Compounds;
Academic Press: New York, 1981.
3. Murahashi, S.-I.; Naota, T.; Miyaguchi, N.; Noda, S. J. Am. Chem. Soc. 1996, 118,
2509.
10
O
CH3
CH3
PdCl2(PhCN)2 (cat.)
SnBr2
CH3
3
DMF
CH3
vitamin K1 (12)
50 ºC, 24 h
O
Scheme 4.
4. Sies, H.; Packer, L. Quinones and Qinone Enzymes; Elsevier Academic Press: San
Diego, 2004; (b) Thomson, R. H. Naturally Occurring Quinones, 3rd ed.; Academic
Press: New York, 1987; (c) The Chemistry of Quinoid Compounds; Patai, S.,
Rappoport, Z., Eds.; Wiley: New York, 1988; Vol. 2, pp 241–402. Part 1.
5. (a) Pilkington, J. W.; Waring, A. J. J. Chem. Soc., Perkin Trans. 2 1976, 1349; For
reviews, see: (b) Moulay, S. Chem. Ed. Res. Pract. Eur. 2002, 3, 33.
6. Dowd, P.; Hershline, R.; Ham, S. W.; Naganthan, S. Science 1995, 296, 1684.
7. (a) Fieser, L. F. J. Biol. Chem. 1940, 133, 391; (b) Juaristi, M.; Aizpurua, J. M.;
Lecea, B.; Palomo, C. Can. J. Chem. 1984, 62, 2941; (c) Periasamy, M.; Bhatt, M. V.
Tetrahedron Lett. 1978, 46, 4561; (d) Asakawa, Y.; Matsuda, R.; Tori, M.; Sono,
M. J. Org. Chem. 1988, 53, 5453; (e) Kol, M.; Rosen, S. J. Org. Chem. 1993, 58,
1593.
8. (a) Shi, F.; Tse, M. K.; Beller, M. Adv. Synth. Catal. 2007, 349, 303; (b) Kholdeeva,
O. A.; Zalomaeva, O. V.; Sorokin, A. B.; Ivanchikova, I. D.; Pina, C. D.; Rossi, M.
Catal. Today 2007, 121, 58.
9. (a) Matveev, K. I.; Odyakov, V. F.; Zhizhina, E. G. J. Mol. Catal. 1996, 114, 151; (b)
Tanoue, Y.; Sakata, K.; Hashimoto, M.; Morishita, S. I.; Hamada, M. Bull. Chem.
Soc. Jpn. 1994, 67, 2593.
regio-isomers and others. The preparation of vitamin K3 has been
carried out simply by stoichiometric7 or catalytic8 oxidations of
2-methylnaphthalene; however, selective formation without
undesired by-product such as 6-methylnaphthoquinone cannot
be achieved.9
One of the important features of our strategy is the flexibility of
the scheme, that is, easy introduction of any substituents at any
position, which enables selective synthesis of various vitamin K3
derivatives with any substituents as shown in Scheme 3.
Vitamin K3 has been used as an intermediate for the synthesis of
vitamin K1 and K2.10 We examined the direct coupling of vitamin
K3 (10) and phytol (11) to give vitamin K1 (12). Although BF3ꢀOEt2
is not efficient for this purpose, we succeeded in the direct reaction
of 10 with 11 using palladium catalyst and tin(II) bromide
(Scheme 4).11 Thus, the reaction of 10 (1.0 mmol) and 11
(2.0 mmol) in the presence of PdCl2(PhCN)2 (0.1 mmol) and SnBr2
(4.0 mmol) in DMF (3 mL) at 50 °C for 24 h gave 12 in 46% isolated
yield.12 This is the first example for the direct synthesis of vitamin
K1 from the corresponding quinone and allyl alcohol. Further
mechanistic study is in progress in our laboratory.
10. (a) Bruckner, N. I.; Bauld, N. L. J. Org. Chem. 1972, 37, 2359; (b) Sato, K.; Inoue,
S.; Saito, K. J. Chem. Soc., Chem. Commun. 1972, 953; (c) Tabushi, I.; Fujita, K.;
Kawakubo, H. J. Am. Chem. Soc. 1977, 99, 6456; (d) Tachibana, Y. Chem. Lett.
1977, 901; (e) Raynolds, P. W. R.; Manning, M. J.; Swenton, J. S. J. Chem. Soc.,
Chem. Commun. 1977, 499; (f) Naruta, Y.; Maruyama, K. Chem. Lett. 1979, 881;
(g) Lipshutz, B. H.; Kim, S.; Mollard, P.; Stevens, K. L. Tetrahedron 1998, 54,
1241.
11. Palladium-catalyzed carbonyl allylation, see: Masuyama, Y.; Takahara, J. P.;
Kurusu, Y. J. Am. Chem. Soc. 1988, 110, 4473.
12. 2,3-Benzo-5-methyl-5-phytylcyclohexane-1,4-dione is also formed in 42%
yield as a regioisomer of vitamin K1. 1H NMR (270 MHz, CDCl3) d 0.80–0.88
(m, 12H), 1.03–1.55 (m, 19H), 1.29 (s, 3H), 1.48 (s, 3H), 1.89 (t, J = 7.1 Hz, 2H),
2.28 (dd, J = 14.2 and 7.6 Hz, 1H), 2.46 (dd, J = 14.2 and 7.6 Hz, 1H), 2.84 (d,
J = 16.1 Hz, 1H), 3.03 (d, J = 16.1 Hz, 1H), 5.04 (t, J = 7.6 Hz, 1H), 7.68–7.78 (m,
2H), 7.98–8.11 (m, 2H). HRMS (EI) m/z calcd for C31H48O2: 452.3654. Found:
452.3634.
Acknowledgments
This work was supported in part by the Research for the Future
Program of the Japan Society for the Promotion of Science and by a