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Synlett 2009(15): 2441-2444  
DOI: 10.1055/s-0029-1217737
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

An Expedient Total Synthesis of (-)-Cladospolide A

Krishna P. Kaliappan*, Debjani Si
Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India
Fax: +91(22)25723480; e-Mail: kpk@chem.iitb.ac.in;
Further Information

Publication History

Received 24 June 2009
Publication Date:
27 August 2009 (online)

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Abstract

A simple and efficient total synthesis of (-)-cladospolide A is described here, which involves either olefin cross metathesis or Julia-Kocienski olefination and Yamaguchi macrolactonization as key steps.

Key words

olefin cross metathesis - Julia-Kocienski olefination - macrolactonization - cladospolides - total synthesis

    References and Notes

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16

Spectral Data for Selected Compounds
Compound 22: R f  = 0.28 (2% EtOAc in hexane); [α]D ²0
-27.6 (c 0.50, CHCl3). IR (neat): 3020, 2931, 1657, 1216, 1045, 669 cm-¹. ¹H NMR (400 MHz, CDCl3): δ = 5.45-5.42 (2 H, m), 4.09-4.05 (3 H, m), 3.80-3.74 (1 H, m), 3.66 (1 H, dd, J = 11.3, 4.8 Hz), 2.13-2.03 (4 H, m), 1.63-1.53 (2 H, m), 1.40 (3 H, s), 1.31 (3 H, s), 1.10 (3 H, d, J = 6.1 Hz), 0.90 (9 H, s), 0.88 (9 H, s), 0.86 (9 H, s), 0.11 (3 H, s), 0.08 (3 H, s), 0.06 (6 H, s), 0.04 (3 H, s), 0.03 (3 H, s). ¹³C NMR (100 MHz, CDCl3): δ = 132.0, 127.2, 107.8, 77.4, 76.4, 72.6, 68.8, 65.3, 43.0, 30.1, 29.1, 28.4, 26.0, 25.96, 25.90, 23.3, 18.4, 18.1, -3.5, -4.5, -4.6, -4.7, -5.3, -5.4.
Compound 23: R f  = 0.26 (2% EtOAc in hexanes); [α]D ²0
-29.7 (c 0.66, CHCl3). IR (neat): 3021, 2930, 2858, 2640, 1380, 1216, 1044, 669 cm-¹. ¹H NMR (400 MHz, CDCl3): δ = 4.08-4.04 (2 H, m), 3.79-3.73 (3 H, m), 3.68-3.64 (1 H, m), 1.65-1.24 (10 H, complex m), 1.39 (3 H, s), 1.30 (3 H, s), 1.09 (3 H, d, J = 6.1 Hz), 0.90 (9 H, s), 0.87 (9 H, s), 0.85 (9 H, s), 0.10 (3 H, s), 0.07 (3 H, s), 0.05 (6 H, s), 0.037 (3 H, s), 0.033 (3 H, s). ¹³C NMR (100 MHz, CDCl3): δ = 107.7, 76.6, 72.6, 68.5, 65.3, 39.6, 30.0, 29.8, 28.4, 26.1, 26.0, 25.96, 25.90, 23.8, 18.4, 18.2, 18.1, -3.5, -4.4, -4.7,
-4.8, -5.3, -5.4. HRMS (EI): m/z calcd for [C32H70O5Si3 + Na]+ : 641.4429; found: 641.4412.
Compound 6: R f  = 0.34 (10% EtOAc in hexanes); [α]D ²0
-12.7 (c 0.83, CHCl3). IR (neat): 3020, 2937, 2401, 1712, 1382, 1216, 1023, 669 cm-¹. ¹H NMR (400 MHz, CDCl3): δ = 6.96 (1 H, dd, J = 15.7, 9.1 Hz), 6.05 (1 H, d, J = 15.8 Hz), 5.08-5.15 (1 H, m), 4.68 (1 H, dd, J = 8.8, 6.4 Hz), 4.10 (1 H, ddd, J = 7.9, 6.1, 1.8 Hz), 1.73-1.61 (2 H, m), 1.54-1.20 (7 H, m), 1.48 (3 H, s), 1.34 (3 H, s), 1.27 (3 H, d, J = 6.4 Hz), 0.98-0.92 (1 H, m). ¹³C NMR (100 MHz, CDCl3): δ = 166.9, 145.1, 124.3, 109.4, 79.5, 76.4, 72.7, 33.3, 30.7, 28.1, 27.9, 25.4, 21.8, 20.0, 18.3.
(-)-Cladospolide A (1): R f  = 0.19 (50% EtOAc in hexanes); mp 90-92 ˚C; [α]D ²0 -40.4 (c 0.50, CHCl3). IR (KBr): 3437, 2927, 2870, 1713, 1651, 1462, 1377, 1269, 1165, 1021, 880 cm-¹. ¹H NMR (400 MHz, CDCl3): δ = 6.80 (1 H, dd, J = 16.0, 5.5 Hz), 6.20 (1 H, dd, J = 16.0, 1.5 Hz), 5.15-5.08 (1 H, m), 4.55-4.53 (1 H, m), 3.65 (1 H, ddd, J = 9.1, 1.8, 1.2 Hz), 1.81-1.11 (9 H, complex m), 1.27 (3 H, d, J = 6.4 Hz), 0.90-0.84 (1 H, m). ¹³C NMR (100 MHz, CDCl3): δ = 167.9, 145.5, 122.2, 74.6, 72.9, 72.8, 32.3, 30.6, 28.1, 25.0, 22.5, 18.9.