2
4
-Substituted Quinones from p-Substituted Phenols
H), 2.40 (m, 4 H), 2.92 (ddd, J = 24.1, 6.5, 2.2 Hz, 1 H), 3.14
25.2, 26.0, 28.0, 32.6, 32.8, 36.6, 37.26, 37.35, 37.38, 37.44, 39.4,
(
ddd, J = 24.1, 4.6, 2.2 Hz, 1 H), 3.41 (m, 1 H), 5.77 (m, 2 H) ppm. 40.0, 118.8, 133.26, 133.31, 137.9, 143.3, 146.2, 184.5, 185.5 ppm.
13
+
C NMR (68 MHz, CDCl
38.7, 130.1, 121.3, 28.8, 24.0, 22.5, 22.4, 21.9, 21.2, 21.1 ppm.
3
): δ = 187.1, 186.6, 143.5, 142.2, 141.7, HRMS (EI): calcd. for C31
Data for 2,3-benzo-5-methyl-5-phytylcyclohexane-1,4-dione:
0.50 (SiO ; hexane/ethyl acetate, 10:1). IR (neat): ν˜ = 3071, 2926,
698, 1597, 1462, 1414, 1377, 1316, 1291, 1258, 1213, 1159, 1063,
46 2
H O [M] 450.3498; found 450.3491.
[
27]
1
R
f
=
1
9
2
Sc(OTf) -Catalyzed Diels–Alder Reaction of Toluquinone (3a)
3
and 1,3-Butadiene. Synthesis of 2-Methyl-5,8,9,10-tetrahydro-1,4-
–1 1
80, 920, 799, 756, 725, 694 cm . H NMR (270 MHz, CDCl
3
): δ
0.80–0.88 (m, 12 H), 1.03–1.55 (m, 19 H), 1.29 (s, 3 H), 1.48 (s,
H), 1.89 (t, J = 7.1 Hz, 2 H), 2.28 (dd, J = 14.2, 7.6 Hz, 1 H),
naphthoquinone (36):[ To a suspension of Sc(OTf)
46]
(10 mol-%) in
3
=
3
CH NO (2.5 mL) was added a mixture of 3a (0.122 g, 1.0 mmol)
and 1,3-butadiene (0.25 mL, 3.0 mmol) at 0 °C. The mixture was
stirred at room temperature for 2 h and quenched by the addition
of a saturated aqueous solution of NaHCO
layer was extracted with ethyl acetate (3ϫ4 mL), and the combined
organic layers were dried with Na SO . Evaporation of the solvent
gave 36 (0.174 g, 99%); m.p. 86.0–86.5 °C (ref.
IR (KBr): ν˜ = 3029, 2924, 1674, 1620, 1443, 1431, 1379, 1368, 1345,
3
2
2.46 (dd, J = 14.2, 7.6 Hz, 1 H), 2.84 (d, J = 16.1 Hz, 1 H), 3.03
(
d, J = 16.1 Hz, 1 H), 5.04 (t, J = 7.6 Hz, 1 H), 7.68–7.78 (m, 2
3
(4 mL). The aqueous
13
H), 7.98–8.11 (m, 2 H) ppm. C NMR (68 MHz, CDCl
3
): δ =
1
3
1
6.1, 19.67, 19.72, 22.6, 23.8, 24.4, 24.8, 25.2, 28.0, 32.6, 32.8, 36.6,
7.26, 37.32, 37.35, 37.40, 39.3, 40.2, 49.5, 49.7, 118.2, 125.9, 127.4,
2
4
[46]
m.p. 80–81 °C).
33.8, 134.1, 134.3, 134.4, 135.0, 196.5, 200.9 ppm. HRMS (EI):
+
calcd. for C31
H
48
O
2
[M] 452.3654; found 452.3634.
–1 1
1
(
327, 1283, 1204, 1088, 1046, 986, 922, 899, 648 cm . H NMR
270 MHz, CDCl ): δ = 2.00 (d, J = 1.5 Hz, 3 H), 2.12 (m, 2 H),
.41 (m, 2 H), 3.21 (m, 1 H), 3.21 (m, 1 H), 5.69 (dd, 2 H), 6.53
): δ = 16.2,
4.3, 46.2, 46.4, 124.4, 124.4, 136.1, 148.9, 199.8, 200.3 ppm.
3
2
(
Acknowledgments
q, J = 1.5 Hz, 1 H) ppm. 13C NMR (67.9 MHz, CDCl
3
2
+
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 Grant-in-Aid for Scientific Research from the Ministry of Educa-
HRMS (EI): calcd. for C11
12 2
H O [M] 176.0837; found 176.0857.
Synthesis of Vitamin K
3
(37).[47] Pd/C-Catalyzed Dehydrogenation
of 2-Methyl-5,8,9,10-tetrahydro-1,4-naphthoquinone (36) in Acetone: tion, Culture, Sports, Science, and Technology of Japan.
A 10 mL sealed tube equipped with a magnetic stir bar was charged
with 36 (0.035 g, 0.20 mmol), 10% Pd/C (22.0 mg, 0.02 mmol) and
[
1] a) P. R. O. Montellano in Cytochrome P-450 Structure, Mecha-
acetone (2.0 mL) under argon. The mixture was stirred at reflux
temperature for 24 h, then filtered through a pad of Celite. Evapo-
ration of the solvent gave 37 (0.034 g, 100%) as a yellow solid; m.p.
nism, and Biochemistry, 2nd ed., Plenum Press, New York,
1995, pp. 245–303; b) W. I. Taylor, A. R. Battersby in Oxidative
Coupling of Phenols, Marcel Dekker, New York, 1967; c) K. U.
Ingold in Free Radicals (Ed.: J. K. Kochi), John Wiley & Sons,
New York, 1973, vol. 1, pp. 37–112; d) R. A. Sheldon, J. K.
Kochi in Metal-Catalyzed Oxidations of Organic Compounds,
Academic Press, New York, 1981; e) D. A. Whiting in Compre-
hensive Organic Synthesis (Ed.: B. M. Trost), Pergamon, Ox-
ford, 1991, vol. 3, pp. 659–703.
[
47]
1
06.0–107.0 °C (ref.
m.p. 107 °C). IR (KBr): ν˜ = 3069, 1665,
–
1
1
624, 1595, 1354, 1302, 1267, 1157, 1019, 941, 779, 693, 667 cm .
H NMR (270 MHz, CDCl ): δ = 2.19 (d, J = 1.5 Hz, 3 H), 6.84
3
1
(q, J = 1.5 Hz, 1 H), 7.71 (d, J = 5.9 Hz, 1 H), 7.72 (d, J = 5.6 Hz,
1
1
1
H), 8.06 (dd, J = 10.4, 5.61 Hz, 1 H), 8.07 (dd, J = 10.4, 5.9 Hz,
H) ppm. 1 C NMR (67.9 MHz, CDCl
3
3
): δ = 16.4, 126.1, 126.5,
[
[
[
2] For RuCl
3 2
/H O, see: a) S. Ito, K. Aihara, M. Matsumoto, Tet-
32.2, 132.3, 133.5, 133.6, 135.7, 148.2, 184.9, 185.5 ppm. HRMS:
II
+
rahedron Lett. 1983, 24, 5249–5252; For Ru /H O, see: b) S.
2
m/z: calcd. for C11
H
8
O
2
[M ]; 172.0524; found 172.0536.
Iwasa, A. Fakhruddin, H. S. Widagdo, H. Nishiyama, Adv.
Synth. Catal. 2005, 347, 517–520.
Synthesis of Vitamin K
1
(39). Palladium-Catalyzed Allylation of Vi-
3] For Fe(salan)/O
2
, see: a) H. Egami, T. Katsuki, J. Am. Chem.
/O , see: b) M. Matsu-
3
tamin K (37) with Phytol (38) in the Presence of Tin(II) Bromide:
A side-armed round-bottomed flask (25 mL) equipped with a mag-
netic stir bar and a three-way stopcock was charged with 37
Soc. 2009, 131, 6082–6083; for Ru(OH)
shita, K. Kamata, K. Yamaguchi, N. Mizuno, J. Am. Chem.
x
2
Soc. 2005, 127, 6632–6640.
(
172 mg, 1.0 mmol), 38 (593 mg, 2.0 mmol), and dimethylform-
amide (DMF, 3.0 mL) under argon at room temperature. The mix-
ture was stirred at room temperature, and PdCl (PhCN) (38.4 mg,
.10 mmol) and tin(II) bromide (1114 mg, 4.0 mmol) were added.
II
4] For Pt /H
2
O
2
, see: a) A. Marsella, S. Agapakis, F. Pinna, G.
I
2
Strukul, Organometallics 1992, 11, 3578–3587; for Cu /O , see:
2
2
b) M. Maumy, P. Capdevielle, J. Mol. Catal. A 1996, 113, 159–
166; for IBX (o-iodoxybenzoic acid), see: c) D. Magdziak,
A. A. Rodriguez, R. W. Van De Water, T. R. R. Pettus, Org.
0
The mixture was stirred at room temperature for 24 h and then
quenched by the addition of an aqueous solution of 10% HCl
Lett. 2002, 4, 285–288.
II
[
[
5] For Cu /O
2
, see: a) J. Tsuji, H. Takayanagi, J. Am. Chem. Soc.
(
(
5.0 mL). The aqueous layer was extracted with ethyl acetate
3ϫ5.0 mL). The combined organic layers were washed with a sat-
1
974, 96, 7349–7350; b) M. M. Rogic, T. R. Demmin, J. Am.
III
Chem. Soc. 1978, 100, 5472–5487; for Fe /CH
S. R. Kaschabek, W. Reineke, J. Org. Chem. 1994, 59, 4001–
003.
3 3
CO H, see: c)
urated aqueous solution of NaHCO
3
(10 mL) and brine (10 mL)
and then dried with Na SO . Evaporation of the solvent gave a
2
4
4
dark brown oil (1048 mg). Purification by preparative TLC gave 39
as a yellow oil (209 mg, 46%) and 2,3-benzo-5-methyl-5-phytylcy-
clohexane-1,4-dione as a pale yellow oil (192 mg, 42%). Data for
6] a) S. Quideau, L. Pouységu, D. Deffieux, Synlett 2008, 467–
495; b) S. Yamamura, S. Nishiyama, Synlett 2002, 533–543; c)
T. Bach, Angew. Chem. 1996, 108, 795–796; Angew. Chem. Int.
Ed. Engl. 1996, 35, 729–730; d) P. W. Rabideau, Z. Marcinow,
Org. React. 2004, 42, 1–334; e) J. Cornelisse, Chem. Rev. 1993,
[
33a]
compound 39:
f 2
R = 0.57 (SiO ; hexane/ethyl acetate, 10:1). IR
(neat): ν˜ = 3015, 2919, 2870, 1661, 1618, 1597, 1462, 1377, 1331,
9
3, 615–619.
1
7
296, 1258, 1229, 1173, 1159, 1136, 1094, 1070, 972, 949, 893, 787,
14, 693, 666, 639 cm . H NMR (270 MHz, CDCl ): δ = 0.81 (d,
3
II
–1
1
2 2
[7] For Fe /H O , see: a) S. L. Cosgrove, W. A. Waters, J. Chem.
Soc. 1951, 1726–1730; for Co/tBuOOH, see: b) E. C. Horswill,
K. U. Ingold, Can. J. Chem. 1966, 44, 269–277.
J = 6.6 Hz, 3 H), 0.82 (d, J = 6.4 Hz, 3 H), 0.86 (d, J = 6.6 Hz, 6
H), 0.96–1.57 (m, 19 H), 1.78 (d, J = 1.2 Hz, 3 H), 1.94 (t, J =
[8] For Cu/tBuOOH, see: a) W. H. Richardson, J. Am. Chem. Soc.
7
7
.7 Hz, 2 H), 2.19 (s, 3 H), 3.37 (d, J = 7.1 Hz, 2 H), 5.00 (tq, J =
1
966, 88, 975–979; for heteropolyacid/tBuOOH, see: b) M. Shi-
1
3
.1, 1.2 Hz, 1 H), 7.65–7.74 (m, 2 H), 8.05–8.12 (m, 2 H) ppm.
C
mizu, H. Orita, T. Hayakawa, Y. Watanabe, K. Takehira, Bull.
Chem. Soc. Jpn. 1991, 64, 2583–2584.
NMR (68 MHz, CDCl
3
): δ = 12.7, 16.3, 19.7, 22.6, 22.7, 24.4, 24.8,
Eur. J. Org. Chem. 2011, 5355–5365
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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