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Synlett 2006(19): 3340-3342  
DOI: 10.1055/s-2006-951540
LETTER
© Georg Thieme Verlag Stuttgart · New York

A Short and Efficient Preparation of Enantiopure Secosyrins 1 and 2

Alexandros E. Koumbis*, Anastasia-Aikaterini C. Varvogli
Laboratory of Organic Chemistry, Department of Chemistry, Aristotle University of Thessaloniki, Thessaloniki 541 24, Greece
Fax: +30(2310)997679; e-Mail: akoumbis@chem.auth.gr;
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Publication History

Received 9 September 2006
Publication Date:
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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  • 14a

    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.

  • 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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10

Preliminary results of this work were presented at the 1st European Chemistry Congress, Budapest, Hungary, August 2006, p. 329 (N-PO-94).

16

The 3-O-TBS derivative instead of the 3-O-benzyl derivative (12).

17

Compound 15 was found to have identical physical and spectra data with those reported in ref. 7c.

18

Compounds 2a and 2b were found to have physical and spectral data identical to those reported in ref. 7a.

19

To the best of our knowledge, these are the highest overall yields reported so far for the total synthesis of both secosyrins.