LETTER
Synthetic Studies towards Iriomoteolide-1a
2471
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OTBDPS
OTBS
a
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+
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5
6
OTBS
19
OTBDPS
OTBS
b, c
H
OTBS
O
4
Scheme 4 Reagents and conditions: a) 6, LiHMDS, DMF–HMPA,
–40 °C, 10 min; then 5, warm to r.t., 50%; b) HF·py, pyridine, THF,
r.t., 80%; c) TPAP, NMO, 4 Å MS, CH2Cl2, 90%.
group in 19 in the presence of HF·py and subsequent Ley
oxidation afforded the desired aldehyde 4 in 72% yield
over the two steps.16
(4) Tsuda, M.; Oguchi, K.; Iwamoto, R.; Okamoto, Y.;
Kobayashi, J.; Fukushi, E.; Kawabata, J.; Ozawa, T.;
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In conclusion, we have developed a highly stereocon-
trolled synthesis of the C13–C23 segment 4 of iriomo-
teolide-1a in eleven steps and 21% overall yield in the
longest linear sequence from methyl ketone 11 featuring a
highly selective Julia–Kocienski coupling. Further inves-
tigations directed toward the total synthesis of iriomo-
teolide-1a are currently under way in our laboratory.
(8) Corey, E. J.; Guzman-Perez, A.; Noe, M. C. J. Am. Chem.
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Supporting Information for this article is available online at
(9) Aldehyde 5: [a]D22 –6.4 (c 1.01, CHCl3). IR (film): 2956,
2929, 2858, 1740, 1472, 1255, 1108, 837, 777 cm–1. 1H
NMR (300 MHz, CDCl3): d = 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): d = 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.
(10) Hopkins, M. H.; Overman, L. E.; Rishton, G. M. J. Am.
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Acknowledgment
We are grateful to National Natural Science Foundation of China
for financial support (No.20172064, 203900502, 20532040), QT
program, Shanghai Natural Science Council, and Excellent Young
Scholars Foundation of National Natural Science Foundation of
China (20525208).
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References and Notes
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(14) Sulfone 6: [a]D24 –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): d = 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): d = 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.
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(16) Aldehyde 4: [a]D24 –22.6 (c 0.66, CHCl3). IR (film): 3584,
3072, 3050, 2956, 2930, 2893, 2858, 1472, 1463, 1428,
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Synlett 2009, No. 15, 2469–2472 © Thieme Stuttgart · New York