Total synthesis of the mycolactones

Organic Letters

Volumn 4, Issue 4, 2002, Pages 647-650

  Song, Fengbin ^a   Fidanze, Steve ^a   Benowitz, Andrew B ^a,b   Kishi, Yoshito ^a  

^a HARVARD UNIVERSITY   (United States)

^b GLAXOSMITHKLINE   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

DYES, REAGENTS, INDICATORS, MARKERS AND BUFFERS; LACTONE; MYCOLACTONE A; MYCOLACTONE B;

ARTICLE; CHEMISTRY; CONFORMATION; MYCOBACTERIUM ULCERANS; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; SYNTHESIS;

INDICATORS AND REAGENTS; LACTONES; MAGNETIC RESONANCE SPECTROSCOPY; MOLECULAR CONFORMATION; MYCOBACTERIUM ULCERANS;

EID: 0037149026     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol0172828     Document Type: Article

References (23)

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8. We recently noticed that the chemical shift assignment for the C19 carbon of 1c and 1d in ref 4a should be revised. Because of this, the graphs shown in Figure 2 in ref 4a should be corrected as included in the Supporting Information of this paper.
9. For the numbering adopted in this paper, see the structures in Figure 1.
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15. 1H NMR analysis).
16. The details for structural correlation of 9 with the authentic sample reported in ref 4b is included in Supporting Information.
17. 3, 500 MHz) of (2′E,4′E,6′E)-11: δ 7.35 ppm (1H, d, J = 16.0 Hz), 6.28 (1H, s), 5.89 (1H, d, J = 15.5), 5.52 (1H, m), 4.12 (4H, m), 3.77 (3H, s), 2.72 (2H, dd, J = 22.5, 7.5), 1.95 (3H, s), 1.86 (3H, d, J = 4.0), 1.33 (6H, t, J = 7.0).
18. The stereochemistry of geometric isomers was assigned via NOE experiments on the olefinic protons.
19. 6) is diagnostic to differentiate these geometric isomers: δ 7.35 ppm (d, J =15.5 Hz) for (2′E,4′E,6′E,8′E,10′E)-12; 7.92 (d, J = 15.5) for (2′E,4′Z,6′E,8′E,10′E)-12; 7.36 (d, J = 15.5) for (2′E,4′E,6′Z,8′E,10′E)-12; 7.43 (d, J = 15.5) for (2′E,4′Z,6′Z,8′E,10′E)-12. The fifth isomer observed after photolysis seemed to be a mixture of two geometric isomers, corresponding to (2′E,4′E,6′E, 8′E,10′Z)-12 and (2′E,4′Z,6′E,8′E,10′Z)-12. In addition to the H3′ proton, the H11′ resonance is diagnostic to assign the structure for these isomers: δ 5.58 ppm (d, J = 8.5 Hz) for (2′E,4′E,6′E,10′Z)-12 and 5.62 (d, J = 8.5) for (2′E,4′Z,6′E,10′Z)-12; 5.67 (d, J = 8.5) for (2′E,4′E,6′E,10′E)-12 and 5.66 (d, J = 8.5) for (2′E,4′Z,6′E,10′E)-12.
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22. No esterification was observed with EDCI/DMAP or BOP/DMAP.
23. Byproduct formation appeared to be initiated by a Michael addition of a hydroxyl group, followed by a secondary Michael addition(s), and resulted in a complex mixture of the side products. Attempted base- and acid-treatments yielded only a trace amount of the desired products.