CLUSTER
S. J. Polym. Sci., Part A: Polym. Chem. 2005, 43, 6287.
Preparation of Chiral Dinuclear Vanadium(V) Complex
1669
VOSO4·H2O (952 mg, 5.84 mmol), MS 3 Å (1.46 g) and
MeOH (50 mL) under O2 (balloon). The reaction mixture
was refluxed, and the consumption of 2 was monitored by
TLC (acetone–hexane, 1:3). The resulting solution was
gradually cooled down to r.t. and filtered through Celite to
remove MS 3 Å. The filtrate was evaporated, and the
resulting black solid was dissolved in CH2Cl2 and washed
with H2O. The organic phase was dried over anhyd Na2SO4
and concentrated in vacuum to give (Ra,S,S)-1 (738 mg,
69%) as a black powder. Compound (Ra,S,S)-1: 1H NMR
(270 MHz, CD3OD): d = 8.96 (s, 2 H, CH=N), 8.48 (s, 2 H,
ArH), 8.06 (t, J = 4.7 Hz, 2 H, ArH), 7.70 (t, J = 4.9 Hz, 2 H,
ArH), 7.44–7.38 (m, 4 H, ArH), 4.23 (s, 2 H, CHt-Bu), 1.25
(s, 18 H, t-Bu). 13C NMR (67.7 MHz, CD3OD): d = 167.9,
138.7, 137.6, 130.6, 130.5, 129.6, 127.4, 125.3, 124.1, 83.8,
38.8, 28.2. 51V NMR (CD3OD): d = –557.2. IR: 3436 (OH),
1683 (C=N), 1608 (C=O), 996 (V=O) cm–1. HRMS–FAB:
m/z calcd for C34H35N2O10V2: 733.1171 [M + H]+; found:
733.1185.
(o) Temma, T.; Hatano, B.; Habaue, S. Tetrahedron 2006,
62, 8559. (p) Temma, T.; Hatano, B.; Habaue, S. Polymer
2006, 47, 1845. (q) Temma, T.; Takahashi, Y.; Yoshii, Y.;
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Chem. Commun. 2001, 980. (c) Barhate, N. B.; Chen, C.-T.
Org. Lett. 2002, 4, 2529. (d) Luo, Z.; Liu, Q.; Gong, L.; Cui,
X.; Mi, A.; Jiang, Y. Chem. Commun. 2002, 914. (e) Luo,
Z.; Liu, Q.; Gong, L.; Cui, X.; Mi, A.; Jiang, Y. Angew.
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T.; Kantam, L. K.; Iwasawa, Y. Chem. Comunn. 2004,
2542. (i) Tada, M.; Kojima, N.; Izumi, Y.; Taniike, T.;
Iwasawa, Y. J. Phys. Chem. B 2005, 109, 9905. (j) Habaue,
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L.-Z. J. Am. Chem. Soc. 2007, 129, 13927.
(7) The catalyst 1 prepared by the two-step promoted coupling
reaction of 2-naphthol to afford (S)-BINOL with 96% yield
and 85% ee in 24 h at r.t. under air.
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65, 1010.
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Commun. 2008, 1810. (b) Takizawa, S.; Katayama, T.;
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(11) Representative Procedure for the Oxidative Coupling of
9-Phenanthrol Using (Ra,S,S)-1
In a round-bottomed flask (500 mL) was taken CH2Cl2 (240
mL) and 9-phenanthrol (5, 6.0 g, 30.9 mmol). Compound
(Ra,S,S)-1 (1.1 g, 1.54 mmol) was charged, and the reaction
vessel was purged with O2 (balloon). The reaction was
stirred for 48 h at –10 °C. A short column to remove the
catalyst gave (S)-4 in quantitative yield with 90% ee. Single
recrystallization of the product thus obtained with hexane–
acetone (5:4) gave optically pure (S)-4 in 79% yield.
Compound (S)-4: >99% ee, [a]D23 –65.7 (c 1.2, CHCl3).
(5) Pawar, V. D.; Bettigeri, S.; Weng, S.-S.; Kao, J.-Q.; Chen,
C.-T. J. Am. Chem. Soc. 2006, 128, 6308.
(6) General Procedure for the One-Pot Preparation of
(Ra,S,S)-1
A round-bottomed flask was charged with (R)-3,3¢-
diformyl-2,2¢-dihydroxy-1,1¢-binaphthyl (2, 500 mg,
1.46 mmol), (S)-tert-leucine (3, 383 mg, 2.92 mmol),
Synlett 2009, No. 10, 1667–1669 © Thieme Stuttgart · New York