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DOI: 10.1055/s-2006-951540
A Short and Efficient Preparation of Enantiopure Secosyrins 1 and 2
Publikationsverlauf
Publikationsdatum:
23. November 2006 (online)
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Abstract
An alternative, short and efficient approach for the preparation of enantiopure secosyrins 1 and 2 is reported here. This uses a d-arabinose derivative as starting material and applies a HWE-IHMA strategy for the construction of the spiro-framework of target molecules.
Key words
secosyrins - d-arabinose - HWE olefination - Michael addition - total synthesis
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Compound 10: oil; [α]D 25 -48.3 (c 1.6, CHCl3). IR (neat): 3032, 2987, 2936, 2890, 1780, 1641, 1455, 1372, 1259, 1213, 1071, 1029, 888, 852, 739, 700 cm-1. 1 H NMR (300 MHz, CDCl3): δ = 7.39-7.30 (m, 5 H), 6.07 (s, 1 H), 4.93 and 4.85 (dABq, J = 18.0, 1.8 Hz, 2 H), 4.67 and 4.51 (ABq, J = 12.2 Hz, 2 H), 4.43 (d, J = 4.9 Hz, 1 H), 4.33 (ddd, J = 7.0, 6.1, 4.9 Hz, 1 H), 4.03 (dd, J = 8.6, 7.0 Hz, 1 H), 3.82 (dd, J = 8.6, 6.1 Hz, 1 H), 1.40 (s, 3 H), 1.34 (s, 3 H). 13C NMR (75 MHz, CDCl3): δ = 172.9, 166.6, 136.7, 128.7, 128.3, 127.9, 118.6, 110.1, 76.10, 75.2, 72.5, 72.1, 65.2, 26.0, 24.9. HRMS (MALDI-FTMS): m/e calcd for C17H20O5Na [M + Na]+: 327.1208; found: 327.1207.
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14b
Compound 14: oil; [α]D 25 -5.3 (c 0.8, MeOH). IR (neat): 3445, 2930, 2910, 1779, 1456, 1398, 1207, 1077, 1012, 741, 699 cm-1. 1 H NMR (300 MHz, CDCl3): δ = 7.40-7.31 (m, 5 H), 4.76 and 4.60 (ABq, J = 12.2 Hz, 2 H), 4.45-4.41 (m, 1 H), 4.37 and 4.28 (ABq, J = 10.4 Hz, 2 H), 4.11 (dd, J = 10.4, 4.9 Hz, 1 H), 3.83 (dd, J = 10.4, 2.5 Hz, 1 H), 3.82 (d, J = 1.8 Hz, 1 H), 2.98 and 2.56 (ABq, J = 18.3 Hz, 2 H), 2.74 (br s, 1 H). 13C NMR (75 MHz, CDCl3): δ = 175.7, 137.1, 128.7, 128.2, 127.7, 87.4, 86.2, 76.5, 74.7, 73.3, 72.5, 35.4. HRMS (MALDI-FTMS): m/e calcd for C14H16O5Na [M + Na]+: 287.0895; found: 287.0894.
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References and Notes
Preliminary results of this work were presented at the 1st European Chemistry Congress, Budapest, Hungary, August 2006, p. 329 (N-PO-94).
16The 3-O-TBS derivative instead of the 3-O-benzyl derivative (12).
17Compound 15 was found to have identical physical and spectra data with those reported in ref. 7c.
18Compounds 2a and 2b were found to have physical and spectral data identical to those reported in ref. 7a.
19To the best of our knowledge, these are the highest overall yields reported so far for the total synthesis of both secosyrins.