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Scheme 2.
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acid. The importance of the naphtholic group in the
dimerization process was further established by reacting
2-methylnaphthalene (5c) with Jones reagent. After 2 h
at room temperature, a clean but low 8% conversion
to 2-methyl-1,4-naphthoquinone (6a) was determined
´
10. (a) Gomez, A.; Cabrera, S.; Carretero, J. C. Org. Lett.
2003, 5, 1333–1336; (b) For a review, see: Chiu, P.;
Lautens, M. Top. Curr. Chem. 1997, 190, 1–84.
11. Jones reagent preparation: CrO3 (13.66 g) in H2O (20 mL)
was placed in a 50 mL volumetric flask. H2SO4 95–98%
(11.5 mL) was added with cooling. The mixture was then
diluted to a total volume of 50 mL with water. 2-(5-
Pentynyl)-1-naphthyl trifluoromethanesulfonate (2a). To a
solution of dihydronaphthol 1a (100 mg, 0.471 mmol) in
acetone (3 mL) cooled to 0 °C was added Jones reagent in
a dropwise manner until disappearance of the starting
material, as monitored by TLC. The reaction was
quenched by the addition of isopropanol, followed by
saturated NaHCO3. The solution was extracted three
times with Et2O and the combined organics were washed
with water, brine, dried over MgSO4, and filtered. The
solvent was removed in vacuo and the residue was
azeotropically dried over benzene and taken directly to
the next step without further purification. Triflation was
carried out using pyridine (225 lL, 2.78 mmol) and triflic
anhydride (141 lL, 0.838 mmol) in CH2Cl2 (2 mL). Puri-
fication by flash chromatography using hexanes–Et2O
(95:5) gave rise to an overall yield of 54% of 2a as a yellow
oil. 1H NMR (500 MHz, CDCl3) d 8.07 (1H, d, J =
8.5 Hz), 7.85 (1H, d, J = 8.2 Hz), 7.81 (1H, d, J = 8.5 Hz),
7.59 (1H, dt, J = 7.7, 0.9 Hz), 7.53 (1H, t, J = 7.5 Hz), 7.41
(1H, d, J = 8.5 Hz), 3.02 (2H, t, J = 7.8 Hz), 2.25 (2H, dt,
J = 7.0, 2.6 Hz), 2.00 (1H, t, J = 2.6 Hz), 1.93 (2H, tt,
J = 7.4, 7.1 Hz); 13C NMR (125 MHz, CDCl3) d 142.3,
133.7, 132.0, 128.6, 127.9, 127.7, 127.7, 126.6, 121.2, 118.8
(CF3, q, J = 318 Hz), 83.4, 69.1, 29.4, 28.7, 18.1. Anal.
Calcd for C16H13F3O3S: C, 56.14; H, 3.83. Found: C,
56.21; H, 3.88. General procedure for the oxidative coupling
of 2-substituted 1,2-dihydro-1-naphthols. Jones reagent was
added dropwise to a solution of 2-substituted 1,2-dihydro-
1-naphthol in acetone cooled at 0 °C, until an orange color
persisted. Two to three additional drops were added to the
resulting mixture. Two work-up procedures were used.
1
by analysis of the crude H NMR and GC-MS. The
requirement for strong acidic conditions was demon-
strated by the incapacity of PCC in dichloromethane
to promote dimerization (Scheme 2).
In summary, a mild and operationally simple protocol
to prepare 3,30-disubstituted 1,10-binaphthyl-4,40-
diols from 2-substituted 1,2-dihydro-1-naphthols was
described.
Acknowledgments
The Natural Sciences and Engineering Research Council
of Canada (NSERC), the Canadian Foundation for
Innovation, the Ontario Innovation Trust, and the Uni-
versity of Waterloo are acknowledged for financial sup-
port. V.E.T. thanks the Government of Ontario for an
OGS, L.G.M. thanks NSERC for an USRA and
R.J.C. thanks the Government of Ontario for scholar-
ships (OGS and OGSST).
References and notes
1. (a) Nising, C. F.; Schmid, U. K.; Nieger, M.; Bra¨se, S.
J. Org. Chem. 2004, 69, 6830–6833; (b) Watanabe, T.;
Tanaka, Y.; Shoda, R.; Sakamoto, R.; Kamikawa, K.;
Uemura, M. J. Org. Chem. 2004, 69, 4152–4158.