Efficient Stereoselective Total Synthesis of (+)-Cryptofolione and the First Synthesis of (-)-Cryptocaryalactone [¹]

Abstract

The stereoselective syntheses of the naturally occurring α-pyrone derivatives (+)-cryptofolione and (-)-cryptocaryalactone were efficiently accomplished by using propane-1,3-diol as the starting material. Keck allylation, Mitsunobu center inversion, and olefin cross metathesis were used as the key steps. (-)-Cryptocarya­lactone was synthesized here for the first time.

Key words

total synthesis - lactones - natural products - Keck allylation - Mitsunobu center inversion - olefin cross metathesis

1

Part 51 in the series ‘Synthetic Studies on Natural Products’

References

• 2a Rychnovsky SD. Chem. Rev.  1995,  95:  2021 
• 2b Jodynis-Liebert J. Murias M. Bloszyk E. Planta Med.  2000,  66:  199 
• 2c Murga J. Falomir E. Marco JA. Org. Lett.  2002,  4:  3447 
• 2d Hagen S. Vara Prasad JVN. Tait BD. Adv. Med. Chem.  2000,  5:  159 
• 2e Inayat-Hussain SH. Annuar BO. Din LB. Ali AM. Ross D. Toxicol. in Vitro  2003,  17:  433 
• 3a Kalesse M. Christmann M. Bhatt U. Quitschalle M. Claus E. Saeed A. Burzlaff A. Kasper C. Haustedt LO. Hofer E. Scheper T. Beil W. ChemBioChem  2001,  2:  709 
• 3b Kalesse M. Christmann M. Synthesis  2002,  981 
• 3c Bialy L. Waldmann H. Chem. Commun.  2003,  1872 
• 3d Buck SB. Hardouin C. Ichikawa S. Soenen DR. Gauss C.-M. Hwang I. Swingle MR. Bonness KM. Honkanen RE. Boger DL. J. Am. Chem. Soc.  2003,  125:  15694 
• 4a Bohlmann F. Suwita A. Phytochemistry  1979,  18:  677 
• 4b Juliawata LD. Kitajima M. Takayama H. Achmad SA. Aimi N. Phytochemistry  2000,  54:  989 
• 4c Drewes SE. Sehlapelo BM. Horn MM. Scott-Shaw R. Sander O. Phytochemistry  1995,  38:  1427 
• 4d Drewes SE. Horn MM. Scott-Shaw R. Phytochemistry  1995,  40:  321 
• 5a Sehlapelo BM. Drewes SE. Scott-Shaw R. Phytochemistry  1994,  37:  847 
• 5b Cavalheiro AJ. Yoshida M. Jodynis-Liebert J. Murias M. Bloszyk E. Phytochemistry  2000,  53:  811 
• 6a Zschocke S. Van Staden JJ. Ethnopharmacology  2000,  71:  473 
• 6b Drewes SE. Horn MH. Mavi S. Phytochemistry  1997,  44:  437 
• 7 Schemda-Hirschmann G. Astuddillo L. Bastida J. Codina C. De Arias AR. Ferrira ME. Inchaustti A. Yaluff G. J. Pharm. Pharmacol.  2001,  53:  563 
• 8 Sturgeon CM. Cinel B. Diaz-Marrero AR. McHardy LM. Ngo M. Andersen RJ. Roberge M. Cancer Chemother. Pharmacol.  2008,  61:  407 
• 9a Matsuoka Y. Aikawa K. Irie R. Katsuki T. Heterocycles  2005,  66:  187 
• 9b Sabitha G. Reddy SSS. Reddy DV. Bhaskar V. Yadav JS. Synthesis  2010,  3453 
• 9c Kumar RN. Mesham HM. Tetrahedron Lett.  2011,  52:  1003 
• 9d Das B. Nagendra S. Reddy CR. Tetrahedron: Asymmetry  2011,  22:  1249 
• 10a Spencer GF. England RE. Wolf RB. Phytochemistry  1984,  23:  2499 
• 10b Drewes SE. Horn MM. Ramesar NS. Ferreira D. Nel RJ.-J. Hutchings A. Phytochemistry  1998,  49:  1683 
• 11a Mori Y. Furukawa H. Chem. Pharm. Bull.  1994,  42:  2161 
• 11b Sabitha G. Bhaskar V. Reddy SSS. Yadav JS. Tetrahedron  2008,  64:  10207 
• 11c Radhakrishna P. Krishnarao L. Reddy KLN. Beilstein J. Org. Chem.  2009,  5:  14 
• 11d Sabitha G. Bhaskar V. Reddy SSS. Helv. Chim. Acta  2010,  93:  329 
• 12a Das B. Veeranjaneyulu B. Balasubramanyam P. Srilatha M. Tetrahedron: Asymmetry  2010,  21:  2762 
• 12b Das B. Balsubramanyam P. Veeranjaneyulu B. Reddy GC. Helv. Chim. Acta  2011,  94:  881 
• 13 Keck GE. Tarbet KH. Geraci LS. J. Am. Chem. Soc.  1993,  115:  8467 
• 14 Mitsunobu O. Synthesis  1981,  1 
• 15 Rychnovsky D. Skalitzky DJ. Tetrahedron Lett.  1990,  31:  945 
• 16a Grubbs RH. Chang S. Tetrahedron  1998,  54:  4413 
• 16b Grubbs RH. Tetrahedron  2004,  60:  7117 

1

Part 51 in the series ‘Synthetic Studies on Natural Products’