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LETTER
(3) Bechtold, T. In Handbook of Natural Colorants; Bechtold,
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O
O
O
O
[Cp*RhCl2]2
+
R
B(OH)2
CH2Cl2–H2O (2:1)
r.t., 10 h
R
(6) Ortega, A.; Rincón, Á.; Jiménez-Aliaga, K. L.; Bermejo-
Bescós, P.; Martín-Aragón, S.; Molina, M. T.; Csákÿ, A. G.
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1 or 4
2
6
O
O
O
(7) Gunatialaka, A. A. L.; Berger, J. M.; Evans, R.; Miller, J. S.;
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Me
n-Bu
O
O
O
6c, 45%
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6a, 39%
6b, 58%
O
O
O
Me
n-Bu
O
O
O
6d, 31%
6e, 42%
6f, 36%
Scheme 4 Substrate expansion of alkyl boronic acids. Reagents and
conditions: benzoquinone or naphthoquinone (0.5 mmol, 1.0 equiv),
alkylboronic acid (1.5 equiv), [Cp*RhCl2]2 (5 mol%), CH2Cl2–H2O
(2:1, 3 mL), 10 h, r.t. Isolated yields are reported.
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Seiple, I. B.; Gianatassio, R.; Bel, M. D.; Baran, P. S. J. Am.
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G.; Zhang, J.; Yu, X.-Q. Chem. Commun. 2012, 48, 11769.
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Org. Chem. 2013, 5251. (e) Singh, P. P.; Aithagani, S. K.;
Yadav, M.; Singh, V. P.; Vishwakarma, R. A. J. Org. Chem.
2013, 78, 2639. (f) Demchuk, O. M.; Pietrusiewicz, K. M.
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8607.
O
O
BBr3, CH2Cl2
–78 °C, r.t.
O
O
OH
OMe
B: 81% yield
5c
Scheme 5 Preparation of BACE1 inhibitor B
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(11) General Procedure for the Reaction of Benzoquinone
with Boronic Acid
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To a solution of benzoquinone (0.5 mmol, 1.0 equiv) and
[Cp*RhCl2]2 (0.025 mmol, 5 mol%) in CH2Cl2 (2 mL) was
added the boronic acid (0.75 mmol, 1.5 equiv), H2O (1 mL).
Then the solution was stirred vigorously at r.t. for 10 h. Upon
completion, the reaction was diluted with CH2Cl2 (3 mL)
and washed with 5% NaHCO3. The layers were separated,
and the aqueous layer was extracted with CH2Cl2 (3 × 4 mL),
dried over Na2SO4, and was evaporated to give the residue.
The residue was then purified by column chromatography on
silica gel (EtOAc–PE, 1:10) to provide the corresponding
product 2-p-tolyl[1,4]benzoquinone (3b). 1H NMR (400
MHz, CDCl3): δ = 7.39 (d, J = 8.2 Hz, 2 H), 7.26 (d, J = 8.0
Hz, 2 H), 6.88–6.77 (m, 3 H), 2.40 (s, 3 H).
Synlett 2014, 25, 2895–2898
© Georg Thieme Verlag Stuttgart · New York