Prebiotic Carbohydrate Synthesis: Zinc-Proline Catalyzes Direct Aqueous Aldol Reactions of α-Hydroxy Aldehydes and Ketones
Jacob Kofoed, Jean-Louis Reymond and Tamis Darbre*
Department of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, CH-3012 Bern, Switzerland.
Fax: +41 31 631 80 57; Tel : +41 31 631 43 70; E-mail: [email protected]
Supporting Information
NMR and GC spectra. tetroses
Figure S1. GC of the peracetylated crude from aldolisation of glycolaldehyde.
β-threose α-threose β-erythrose
Figure S2. GC of the peracetylated crude sugar mixture showing α-threose, β-threose and β- erythrose (time shown in min).
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Integral 1.0000 0.0437 0.6899 0.9642 1.0142 0.3432 3.9561 1.0935 3.3902 1.8681 1.0503 32.517
9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 (ppm)
1 Figure S3. H NMR (500 MHz) in CDCl3 of the tetrose acetate mixture showing α-threose, β- threose and β-erythrose. 2539.59 2535.07 2516.25 2511.73 2448.49 2446.73 2426.15
β-threose β-erythrose α-threose Integral 1.0000 0.0437 0.6899 0.9642 6.48 6.44 6.40 6.36 6.32 6.28 6.24 6.20 6.16 6.12 6.08 6.04 6.00 5.96 5.92 (ppm) 1 Figure S3. H NMR (CDCl3, 500 MHz) showing the anomeric protons of acetylated α-threose, β- threose and β-erythrose.
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5.3202 5.3077 5.2945 5.2499 5.2411 5.2330 4.3419 4.3287 4.3237 4.3023 4.2891 4.2829 4.1994 4.1818 4.1586 4.1404 4.0695 4.0500 4.0293 4.0105 2.0877 2.0732 2.0488 2.0456 1597.02 1593.26 1589.30 1575.93 1573.29 1570.84 1221.58 1215.74 1209.53 1203.87 1299.38 1297.88 1291.47 1287.52 1285.63 1260.58 1255.30 1248.33 1242.87 0.8442 1.9841 1.1425 0.8310 1.0905 1.9841
5.30 5.2 4.3 4.2 (ppm) (ppm) (ppm) (ppm) (ppm) Integral 0.8310 1.0905 1.9841 1.1425 0.8442 12.167
9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 (ppm)
1 Figure S4. H NMR (CDCl3, 300 MHz) of tetrol peracetates.
Commercial L-Threitol tetraacetate Reduced and acetylated tetrol mixture Figure S5. Chiral GC trace of reduced and acetylated tetrols showing the meso-erythritol and the two enantiomers of threitol.
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talose
mixture
Figure S6. Overlaying of reference sugars and crude mixture from the aldolisation of glycolaldehyde (hexose region).
sorbit
mannit
allitol
dulcit
talitol
mixture
Figure S7. Overlaying of reduced reference sugars and crude mixture from the aldolisation of glycolaldehyde (hexose region).
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mixture
Figure S8. Overlaying of reference sugars and crude mixture from the cross-aldolisation of glycolaldehyde and glyceraldehyde.
xylit
arabit+lyxit
adonit
mixture
Figure S9. Overlaying of reduced reference sugars and crude mixture from the cross-aldolisation of glycolaldehyde and glyceraldehyde.
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A
B
C
5.40 5.30 5.20 5.10 5.00 4.90 4.80 4.70 4.60 4.50 4.40 (ppm) D Figure S11. Overlaying of the four different experiments showing the anomeric region. A: ketohexoses, B: ketopentoses, C: tetroses and hexoses, D: tetroses and pentoses.
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