Total Synthesis of (±)-Petasitolone and (±)-Fukinone

Abstract

An efficient, general, and fully stereocontrolled synthesis of eremophilane-type compounds is disclosed. The approach features a highly diastereoselective Diels-Alder/aldol sequence to give a common intermediate, which is subsequently exploited to produce (±)-petasitolone and (±)-fukinone in a short sequence.

Key words

eremophilane - Diels-Alder reactions - aldol reactions - condensation

References

• 1a Devon TK. Scott AI. Handbook of Naturally Occurring Compounds   Vols. I and II:  Academic; New York: 1972. 
• 1b Terpenoids and Steroids   Vols. 1-12:  The Chemical Society; London: 1971-1983. 
• 1c Ho TL. Carbocyclic Construction in Terpene Synthesis   VCH; New York: 1988. 
• 2 For a review on cis-decahydronaphthalene, see: Singh V. Iyer SR. Pal S. Tetrahedron  2005,  61:  9197 
• 3a Glasby JS. Encyclopedia of the Terpenoids   Wiley; Chichester: 1982. 
• For more recent reports on sesquiterpenoids, see:
• 3b Fragan BM. Nat. Prod. Rep.  2003,  20:  392 
• For diterpenoids, see:
• 3c Hanson JR. Nat. Prod. Rep.  2004,  21:  312 
• For triterpenoids, see:
• 3d Connolly JD. Hill RA. Nat. Prod. Rep.  2003,  20:  640 
• 4a Fisher NH. Oliver EJ. Fisher HD. In Progress in the Chemistry of Organic Natural Products   Vol. 38:  Herz W. Grisebach HK. Springer; New York: 1979.  Chap. 2.
• 4b Srikrishna A. Nagaraju S. Venkateswarlu S. Hiremath US. Reddy TJ. Venugopalan P. J. Chem. Soc., Perkin Trans. 1  1999,  2069 
• 4c Fleming FF. Shook BC. Jiang T. Steward OW. Org. Lett.  1999,  1:  1547 
• 4d Silva LF. Synthesis  2001,  671 
• 4e Back TG. Nava-Salgado VO. Payne JE. J. Org. Chem.  2001,  66:  4361 
• 4f Brocksom TJ. Coelho F. Depres JP. Green AE. Freire de Lima ME. Hamelin O. Hartmann B. Kanazawa AM. Wang Y. J. Am. Chem. Soc.  2002,  124:  15313 
• 4g Mehta G. Senthil Kumaran R. Tetrahedron Lett.  2003,  44:  7055 
• 4h Hsu D.-S. Hsu P.-Y. Lee Y.-C. Liao C.-C. J. Org. Chem.  2008,  73:  2554 
• 5 Naya K. Yoshimura F. Takagi I. Bull. Chem. Soc. Jpn.  1971,  44:  3165 
• 6 Naya K. Takagi I. Kawaguchi Y. Asada Y. Hirose Y. Shinoda N. Tetrahedron  1968,  24:  5871 
• 7 Liu H.-J. Ngooi TK. Can. J. Chem.  1984,  62:  2676 
• 8a Piers E. Smillie RD. J. Org. Chem.  1970,  35:  3997 
• 8b Marshall JA. Cohen GM. Tetrahedron Lett.  1970,  11:  3865 
• 8c Torrence AK. Pinder AR. Tetrahedron Lett.  1971,  12:  745 
• 8d Prasad CVC. Chan TH. J. Org. Chem.  1987,  52:  120 
• 8e Reddy DS. Kozmin SA. J. Org. Chem.  2004,  69:  4860 
• 9 Srinivas P. Reddy DS. Shiva Kumar K. Dubey PK. Iqbal J. Das P. Tetrahedron Lett.  2008,  49:  6084 
• 11a Reddy DS. Org. Lett.  2004,  6:  3345 
• 11b Reddy DS. Palani K. Balasubrahmanyam D. Vijju KVB. Iqbal J. Tetrahedron Lett.  2005,  46:  5211 
• 12 Srikrishna A. Krishnan K. J. Org. Chem.  1993,  58:  7751 

10

DRL Publication No. 667-A.