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Synlett 2009(15): 2469-2472  
DOI: 10.1055/s-0029-1217728
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Synthetic Studies towards Iriomoteolide-1a: Construction of the C13-C23 Fragment

Zhengqing Ye, Lisheng Deng, Shan Qian, Gang Zhao*
Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, P. R. of China
Fax: +86(21)64166128; e-Mail: zhaog@mail.sioc.ac.cn;
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Publication History

Received 8 June 2009
Publication Date:
27 August 2009 (online)

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Abstract

A stereoselective synthesis of the C13-C23 segment of iriomoteolide-1a was achieved using, as key steps, a highly stereocontrolled crotylation to build the stereocenters at C18 and C19 and a Julia-Kocienski olefination to establish the C15-C16 E-olefin moiety.

Key words

iriomoteolide-1a - macrolide - dihydroxylation - crotylation - Julia-Kocienski olefination

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9

Aldehyde 5: [α]D ²² -6.4 (c 1.01, CHCl3). IR (film): 2956, 2929, 2858, 1740, 1472, 1255, 1108, 837, 777 cm-¹. ¹H NMR (300 MHz, CDCl3): δ = 9.60 (s, 1 H), 3.66 (m, 2 H), 1.24 (s, 3 H), 0.90 (s, 9 H), 0.87 (s, 9 H), 0.11 (s, 6 H), 0.03 (s, 6 H). ¹³C NMR (75 MHz, CDCl3): δ = 204.5, 80.7, 68.4, 25.8, 25.7, 20.0, 18.2, 18.2, -2.6, -2.6, -5.6, -5.7. ESI-MS: m/z = 387.2 [M + MeOH + Na]+. ESI-HRMS: m/z calcd for C16H36O3Si2Na+ [M + Na]+: 355.2108; found: 355.2095.

14

Sulfone 6: [α]D ²4 -21.4 (c 1.62, CHCl3). IR (film): 3077, 2957, 2929, 2857, 1593, 1498, 1463, 1428, 1379, 1342, 1256, 1153, 1110, 1078, 1035, 951, 835, 774 cm-¹. ¹H NMR (400 MHz, CDCl3): δ = 7.71-7.66 (m, 6 H), 7.61 (m, 3 H), 7.42-7.35 (m, 6 H), 3.95-3.88 (m, 1 H), 3.80-3.77 (m, 1 H), 3.68-3.56 (m, 2 H), 1.99-1.93 (m, 1 H), 1.87-1.82 (m, 1 H), 1.72-1.64 (m, 2 H), 1.45 (m, 1 H), 1.37-1.30 (m, 1 H), 1.03 (s, 9 H), 1.00 (d, J = 7.5 Hz, 3 H), 0.98 (d, J = 6.6 Hz, 3 H), 0.93 (d, J = 6.6 Hz, 3 H), 0.87 (s, 9 H), 0.01 (s, 3 H), -0.02 (s, 3 H). ¹³C NMR (100 MHz, CDCl3): δ = 153.4, 135.9, 135.9, 134.9, 134.0, 133.1, 131.3, 129.6, 129.6, 129.4, 127.6, 127.3, 125.0, 74.5, 72.5, 54.4, 37.0, 36.8, 35.4, 27.0, 25.9, 22.6, 20.3, 19.3, 18.0, 16.1, 14.6, -4.3, -4.5. ESI-MS: m/z = 757.2 [M + Na]+. HRMS (MALDI): m/z calcd for C39H58N4O4Si2SNa+ [M + Na]+: 757.3633; found: 757.3610.

16

Aldehyde 4: [α]D ²4 -22.6 (c 0.66, CHCl3). IR (film): 3584, 3072, 3050, 2956, 2930, 2893, 2858, 1472, 1463, 1428, 1378, 1361, 1255, 1110, 1029, 975, 938, 835, 739, 702
cm-¹. ¹H NMR (500 MHz, CDCl3): δ = 9.33 (s, 1 H), 7.69-7.66 (m, 4 H), 7.43-7.35 (m, 6 H), 5.76-5.70 (m, 1 H), 5.26 (d, J = 15.6 Hz, 1 H), 3.79-3.77 (m, 1 H), 3.58-3. 56 (m, 1 H), 2.10-2.04 (m, 1 H), 1.81-1.75 (m, 1 H), 1.72-1.67 (m, 1 H), 1.57-1.50 (m, 2 H), 1.37 (s, 3 H), 1.26-1.20 (m, 1 H), 1.06 (s, 9 H), 0.96 (d, J = 6.0 Hz, 3 H), 0.93 (s, 9 H), 0.91 (d, J = 6.9 Hz, 3 H), 0.88 (s, 9 H), 0.85 (d, J = 6.9 Hz, 3 H), 0.11 (s, 3 H), 0.10 (s, 3 H), -0.00 (s, 3 H), -0.02 (s, 3 H). ¹³C NMR (100 MHz, CDCl3): δ = 135.9, 135.9, 135.1, 135.0, 134.2, 130.1, 29.5, 129.4, 127.5, 127.3, 75.7, 74.8, 72.6, 71.4, 37.7, 37.0, 35.8, 34.1, 27.1, 25.9, 25.8, 23.6, 19.9, 19.4, 18.1, 15.8, 15.2, -2.3, -4.3, -4.4. ESI-MS: m/z = 749.4 [M + Na]+. HRMS (MALDI): m/z calcd for C42H74O4Si3Na+ [M + Na]+: 749.4803; found: 749.4787.