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

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.

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

References

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<A NAME="RU08903ST-1B">1b</A> Putra SR. Lois LM. Campos N. Boronat A. Rohmer M. Tetrahedron Lett.  1998,  39:  23 ; and references cited therein

For the enzymatic synthesis, see:

<A NAME="RU08903ST-2A">2a</A> Querol J. Grosdemange-Billiard C. Rohmer M. Boronat A. Imperial S. Tetrahedron Lett.  2002,  43:  8265 

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<A NAME="RU08903ST-2E">2e</A> Zhao S. Petrus L. Serianni AS. Org. Lett.  2001,  3:  3819 

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<A NAME="RU08903ST-5">5</A>

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.