Total Synthesis of (+)-Cladospolide A

Abstract

A stereoselective total synthesis of (+)-cladospolide A from d-ribose is described. Key features of the synthesis include olefin cross metathesis and Yamaguchi lactonization.

Key words

cladospolide A - natural products - total synthesis - macrolactone

• References

• 1a Hirota A, Isogai A, Sakai H. Agric. Biol. Chem. 1981; 45: 799
• 1b Hirota A, Sakai H, Isogai A, Kitano Y, Ashida T, Hirota H, Takahashi T. Agric. Biol. Chem. 1985; 49: 903
• 1c Hirota H, Hirota A, Sakai H, Isogai A, Takahashi T. Bull. Chem. Soc. Jpn. 1985; 58: 2147
• 2 Fujii Y, Fukuda A, Hamasaki T, Ichimoto I, Nakajima H. Phytochemistry 1995; 40: 1443
• 3 Zhang H, Tomoda H, Tabata N, Miura H, Namikoshi M, Yamaguchi Y, Masuma R, Omura S. J. Antibiot. 2001; 54: 635
• 4a Mori K, Maemoto S. Liebigs Ann. Chem. 1987; 863
• 4b Maemoto S, Mori K. Chem. Lett. 1987; 109
• 4c Ichimoto I, Sato M, Kirihata M, Ueda H. Chem. Express 1987; 2: 495 ; Chem. Abstr. 1988, 108, 167
• 4d Solladié G, Almario A. Tetrahedron: Asymmetry 1995; 6: 559
• 4e Banwell MG, Jolliffe KA, Loong DT. J, McRae KJ, Vounatsos F. J. Chem. Soc., Perkin Trans. 1 2002; 22
• 4f Kaliappan KP, Si D. Synlett 2009; 2441
• 4g Rajesh K, Suresh V, Selvam JJ. P, Rao CB, Venkateswarlu Y. Synthesis 2010; 1381
• 5a Prasad KR, Gandi VR. Tetrahedron: Asymmetry 2010; 21: 2848
• 5b Prasad KR, Penchalaiah K. Tetrahedron: Asymmetry 2010; 21: 2853
• 5c Prasad KR, Gandi VR. Tetrahedron: Asymmetry 2010; 21: 275
• 5d Prasad KR, Pawar AB. Synlett 2010; 1093
• 5e Prasad KR, Pawar AB. ARKIVOC 2010; (vi): 39
• 5f Prasad KR, Gandi VR, Nidhiry JE, Bhat KS. Synthesis 2010; 2521
• 5g Prasad KR, Gandi VR. Synlett 2009; 2593
• 5h Prasad KR, Gholap SL. J. Org. Chem. 2008; 73: 2
• 5i Prasad KR, Gholap SL. J. Org. Chem. 2008; 73: 2916
• 5j Prasad KR, Swain B. Tetrahedron: Asymmetry 2008; 19: 1134
• 5k Prasad KR, Chandrakumar A. J. Org. Chem. 2007; 72: 6312
• 5l Prasad KR, Dhaware M. Synthesis 2007; 3697
• 5m Prasad KR, Gholap SL. J. Org. Chem. 2006; 71: 3643
• 5n Prasad KR, Gholap SL. J. Org. Chem. 2006; 71: 3643
• 5o Prasad KR, Anbarasan P. Tetrahedron Lett. 2006; 47: 1433
• 5p Prasad KR, Anbarasan P. Tetrahedron: Asymmetry 2006; 17: 850
• 5q Prasad KR, Anbarasan P. Tetrahedron 2006; 62: 8303
• 5r Prasad KR, Anbarasan P. Synlett 2006; 2087
• 6 Prasad KR, Gandi VR. Tetrahedron: Asymmetry 2011; 22: 499
• 7 Paquette LA, Bailey S. J. Org. Chem. 1995; 60: 7849
• 8 Formation of the dimer resulting from the dimerization of (S)-hept-6-en-2-yl acetate is also observed

Hydrogenation under a H₂ atmosphere with 10% Pd/C as catalyst afforded the saturated lactone 14 in 99% yield. Use of Pd/BaSO₄ as a catalyst in the hydrogenation afforded a lactone in which the electron-deficient double bond was hydrogenated. Hydrogenation did not proceed when RhCl(PPh₃)₃ was used as the catalyst. For selective hydrogenation of an electron-rich olefin in a structurally similar macrolactone see:
• 9a Nishioka T, Iwabuchi Y, Irie H, Hatakeyama S. Tetrahedron Lett. 1998; 39: 5597
• 9b Yadav JS, Rao TS, Ravinder K, Reddy BV. S. Synlett 2009; 2828
• 10 For the introduction of unsaturation by selenation and oxidative deselenation strategy in a structurally similar macrolactone see: Chou C.-Y, Hou D.-R. J. Org. Chem. 2006; 71: 9887

Synthesis of 17 via an alternate procedure was reported earlier. See:
• 11a Jäger V, Häfele B. Synthesis 1987; 801
• 11b Tanaka K, Yamano S, Mitsunobu O. Synlett 2001; 1620
• 12a Sharma A, Gamre S, Chattopadhyay S. Tetrahedron: Asymmetry 2009; 20: 1164
• 12b Lin W, Zercher CK. J. Org. Chem. 2007; 72: 4390