2600
G. Kazantzi et al.
LETTER
(8) Coupling Reaction of Ylides 5 and 9 with Arylboronic
Acids 6; General Procedure. A degassed solution of
arylboronic acid (1.1 mmol) and P(t-Bu)3 (0.1 mmol) in
DME–H2O (4:1, 10 mL) was added to a degassed flask
containing a mixture of ylide 5 or 9 (0.5 mmol), LiOH·H2O
(2.7 mmol), and Pd(OAc)2 (6 mg, 4 mmol%) and the
resulting suspension was stirred at r.t. under Ar for 5 h. The
solution was acidified to pH 6 by the addition of 4–5 drops
of acetic acid and excess DME was evaporated. CH2Cl2 (10
mL) was added and the suspension was filtered through filter
paper, which was moistened with CH2Cl2 (1–2 mL). The
filtrate was dried, concentrated, and subjected to column
chromatography (silica gel, hexanes–EtOAc, 3:1) to afford
the coupling products 7 and 10. 2-Hydroxy-3-(3-thienyl)-
1,4-naphthoquinone (7a): Mp 126–127 °C. IR
In summary, the transformation of 2-hydroxyquinones to
their 3-substituted derivatives can be most conveniently
achieved in two steps: formation of their phenyliodonium
ylides3 and Suzuki-type coupling reaction of the latter
with aryl- and alkenylboronic acids. The high yields, the
diversity of both reaction steps, and the possibility of
conducting the second step in water could make this the
method of choice for the preparation of this interesting
class of compounds.
References and Notes
(1) Thomson, R. H. Naturally Occurring Quinones IV; Blackie
Academic & Professional: London, 1997.
(2) Spyroudis, S. Molecules 2000, 5, 1291.
(3) (a) Hatzigrigoriou, E.; Spyroudis, S.; Varvoglis, A. Liebigs
Ann. Chem. 1989, 167. (b) Papoutsis, I.; Spyroudis, S.;
Varvoglis, A. Tetrahedron Lett. 1994, 35, 8449.
(c) Stagliano, K. W.; Malinakova, H. C. J. Org. Chem. 1999,
64, 8034. (d) Emadi, A.; Hardwood, J. S.; Kohanim, S.;
Stagliano, K. W. Org. Lett. 2002, 4, 521. (e) Spyroudis, S.;
Xanthopoulou, N. J. Org. Chem. 2002, 67, 4612.
(4) Koulouri, S.; Malamidou-Xenikaki, E.; Spyroudis, S.;
Tsanakopoulou, M. J. Org. Chem. 2005, 70, 5627.
(5) Kobayashi, K.; Uneda, T.; Kawakita, M.; Morikawa, O.;
Konishi, H. Tetrahedron Lett. 1997, 38, 837.
(KBr): 3322, 1650, 1590 cm–1. 1H NMR (300 MHz, CDCl3):
d = 8.16 (1 H, d, J = 8.0 Hz), 8.10 (1 H, br s), 8.08 (1 H, d,
J = 8.0 Hz), 7.94 (1 H, s), 7.80–7.65 (3 H, m), 7.35 (1 H, d,
J = 4.8 Hz). 13C NMR (75 MHz, CDCl3): d = 183.8, 181.6,
151.5, 135.2, 133.1, 130.0, 129.7, 129.5, 129.1, 127.3,
126.0, 124.0, 123.2, 116.9. MS (EI): m/z (%) = 256 (100)
[M+], 228 (68), 184 (25), 171 (71). Anal. Calcd for
C14H8O3S: C, 65.61; H, 3.15. Found: C, 65.37; H, 3.19.
(9) For a recent review on Suzuki coupling reactions in water,
see: Leadbeater, N. E. Chem. Commun. 2005, 2881.
(10) The coupling reaction was repeated exactly under the
previously described conditions, using 1 mmol of
iodobenzene instead of ylide 5
(6) Zhu, Q.; Wu, J.; Fathi, R.; Yang, Z. Org. Lett. 2002, 4, 3333.
(7) (a) Transylidation reactions of zwitterionic iodonium
compounds are well known, see: Varvoglis, A. In The
Organic Chemistry of Polycoordinated Iodine; VCH: New
York, 1992. (b) In our case the side-reaction with
phosphines is described in Scheme 2.
(11) (a) Perchellet, E. M.; Magill, M. J.; Huang, X.; Brantis, C.
E.; Hua, D. H.; Perchellet, J.-P. Anti-Cancer Drugs 1999, 10,
749. (b) Xanthopoulou, N. J.; Kourounakis, A. P.;
Spyroudis, S.; Kourounakis, P. N. Eur. J. Med. Chem. 2003,
38, 621. (c) Xua, D. H.; Tamura, M.; Huang, X.; Stephany,
H. A.; Helfrich, B. A.; Perchellet, E. M.; Sperfslage, B. J.;
Perchellet, J.-P.; Jiang, S.; Kyle, D. E.; Chiang, P. K. J. Org.
Chem. 2002, 67, 2907.
Synlett 2006, No. 16, 2597–2600 © Thieme Stuttgart · New York