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Synlett 2003(10): 1521-1523
DOI: 10.1055/s-2003-40860
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

A Practical Access to [1-13C]1-Deoxy-d-xylulose and its Derivatives

Hiroshi Okumoto*, Hiroko Katto
Department of Chemistry and Bioscience, Kurashiki University of Science and the Arts, 2640 Nishinoura, Tsurajima, Kurashiki, 712-8505 Japan
Fax: +81(86)4401062; e-Mail: okmt@chem.kusa.ac.jp;
Further Information

Publication History

Received 12 May 2003
Publication Date:
24 July 2003 (online)

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Abstract

A practical synthesis of [1-13C]1-deoxy-d-xylulose and its triacetate and 5-phosphate derivatives is described. The present scheme is developed based on the consideration of the cost efficiency of 13C.

Key words

isotope - labeled compound - stereoselective synthesis - carbohydrates - terpenoids - natural products - biosynthesis

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5

The selected physical data are shown as follows.
4a: 1H NMR (500 MHz): δ = 3.09 (s, 3 H), 3.43 (s, 3 H), 3.63 (dd, J = 5.5, 10.3 Hz, 1 H), 3.69 (dd, J = 5.5, 10.3 Hz, 1 H), 4.06 (dd, J = 5.5, 10.7 Hz, 1 H), 4.43-4.51 (m, 4 H), 4.63-4.76 (m, 2 H), 7.25-7.35 (m, 15 H).
4b: 1H NMR (500 MHz): δ = 3.09 (s, 3 H), 3.44 (s, 3 H), 3.60 (dd, J = 5.4, 10.3 Hz, 1 H), 3.66 (dd, J = 5.2, 10.3 Hz, 1 H), 3.80 (s, 3 H), 4.04 (dd, J = 5.4, 10.7 Hz, 1 H), 4.30-4.40 (m, 2 H), 4.40-4.50 (m, 2 H), 4.60-4.80 (m, 3 H), 6.83 (d, J = 8.5 Hz, 2 H), 7.18 (d, J = 8.5 Hz, 2 H), 7.25-7.34 (m, 10 H).
5a: [α]D 23 -36 (c 0.36, CHCl3). 1H NMR (500 MHz): δ = 2.14 (d, J = 128 Hz, 13CH3), 3.60 (d, J = 6.1 Hz, 2 H), 3.95-3.97 (m, 2 H), 4.39-4.45 (m, 3 H), 4.51 (d, J = 11.6 Hz, 1 H), 4.63 (d, J = 11.6 Hz, 1 H), 4.67 (d, J = 11.9 Hz, 1 H), 7.24-7.34 (m, 15 H).
5b: [α]D 23 -41 (c 1.0, CHCl3). 1H NMR (500 MHz): δ = 2.13 (d, J = 127 Hz, 13CH3), 3.58 (d, J = 6.0 Hz, 2 H), 3.80 (s, 3 H), 3.93-3.96 (m, 2 H), 4.34 (d, J = 11.3 Hz, 1 H), 4.37 (d, J = 11.3 Hz, 1 H), 4.43 (d, J = 11.7 Hz, 1 H), 4.50 (d, J = 11.7 Hz, 1 H), 4.62 (d, J = 11.7 Hz, 1 H), 4.65 (d, J = 11.7 Hz, 1 H), 6.85 (d, J = 8.6 Hz, 2 H), 7.18 (d, J = 8.6 Hz, 2 H), 7.20-7.34 (m, 10 H).
6b: [α]D 23 +35 (c 0.65, CHCl3). 1H NMR (500 MHz): δ = 2.06, 2.08, 2.21 (s, OAc × 3), 2.21 (d, J = 129 Hz, 13CH3), 4.14 (dd, J = 6.6, 11.6 Hz, 1 H), 4.30 (dd, J = 5.8, 11.6 Hz, 1 H), 5.25 (d, J = 3.0 Hz, 1 H), 5.59 (ddd, J = 3.0, 5.8, 6.6 Hz, 1 H).
7: [α]D 23 -18 (c 0.35, CHCl3). 1H NMR (500 MHz): δ = 2.09 (d, J = 128 Hz, 13CH3), 3.85 (d, J = 3.3 Hz, 1 H), 3.92 (ddd, J = 3.3, 5.8, 6.0 Hz, 1 H), 4.06-4.14 (m, 2 H), 4.38 (d, J = 11.5 Hz, 1 H), 4.41 (d, J = 11.5 Hz, 1 H), 4.53 (d, J = 11.5 Hz, 1 H), 4.60 (d, J = 11.5 Hz, 1 H), 4.96-5.03 (m, 4 H), 7.18-7.35 (m, 20 H). 31P NMR: δ = -6.4.