Asymmetric Synthesis of (R)- and (S)-Chromanemethanol
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was treated with p-toluenesulfonic acid monohydrate (12.4 mg,
0.07 mmol) to yield (R)-11 (34.4 mg, 0.11 mmol, 79% yield). The
TLC and spectroscopic data are identical to those of (S)-11; ee
Ͼ99% (tret = 21.2 min).
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General Procedure for the Synthesis of 2-Hydroxymethyl-2,5,7,8-tet-
ramethylchroman-6-ol (12): A catalytic amount of Pd on C (10%)
was added to a solution of compound 11 (8 m) in MeOH and the
mixture was purged with H2 for 5 h. The reaction mixture was fil-
tered through a pad of Celite, the solvent was evaporated under
reduced pressure and the white solid obtained was purified by
chromatography (petroleum ether/EtOAc, 5:1) to give (R)- or (S)-
12 as a white solid. The ee was determined by chiral HPLC analysis
{Diacel Chiralcel OD-H, n-heptane/EtOH, 95:5, 1.0 mL/min,
18 °C, UV: 215 nm, tret[(R)-12] = 16.0 min, tret[(S)-12] = 20.0 min}.
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(S)-2-Hydroxymethyl-2,5,7,8-tetramethylchroman-6-ol [(S)-12]:
Compound (S)-11 (65.6 mg, 0.20 mmol) in MeOH (25 mL) was
treated as described above to yield (S)-12 (42.3 mg, 0.18 mmol,
90% yield), m.p. 128–129 °C (ref.[23] 129.5–131.5 °C), Rf = 0.34 (pe-
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spectroscopic data are in accordance with the literature.[23] 1
H
NMR: δ = 3.64 (dd, J1 = 9.5, J2 = 11.3 Hz, 2 H), 2.71–2.66 (m, 2
H), 2.19 (s, 3 H), 2.14 (s, 3 H), 2.13 (s, 3 H), 2.06–1.98 (m, 1 H),
1.78–1.71 (m, 1 H), 1.24 (s, 3 H) ppm. 13C NMR: δ = 145.1, 144.9,
122.6, 121.4, 118.8, 117.3, 75.1, 69.4, 27.8, 20.4, 20.3, 12.2, 11.9,
11.3 ppm.
(R)-2-Hydroxymethyl-2,5,7,8-tetramethylchroman-6-ol [(R)-12]:
Compound (R)-11 (34.4 mg, 0.11 mmol) in MeOH (12.5 mL). was
treated as described above to yield (R)-12 (22.4 mg, 0.09 mmol,
86% yield). The m.p., TLC and spectroscopic data are identical to
those of (S)-12, ee Ͼ99% (tret = 16.0 min). [α]2D0 = –1.5 (c = 1.0,
EtOH) {ref.[23] [α]2D3 = –1.8 (c = 1.45, EtOH)}.
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Acknowledgments
Financial support by the Fundacion Ramon Areces (Madrid) and
the Austrian Science Fund (FWF, Vienna, W9 DK Molecular En-
zymology) is gratefully acknowledged. Birgit Seisser, Jörg Schritt-
wieser and Wolfgang Kroutil are thanked for helpful hints and dis-
cussions.
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© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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