Acid-Catalyzed Rearrangement of an Allene-Cyclohexenone Photoadduct and its Application in the Synthesis of (±)-Pentalenene

Abstract

The acid-catalyzed rearrangement of 3-methylenetricyclo[6.3.0.0^1.4]undecan-5-one (5), prepared via the photocycloaddition of cyclohexenone to allene, gave the triquinanes. In addition, the method was applied to the synthesis of (±)-pentalenene.

Keywords

rearrangement - allene - cyclohexenone - total synthesis - pentalenene

References

• 1a Kakiuchi K. Ue M. Takahara H. Shimizu T. Miyao T. Tobe Y. Odaira Y. Yasuda M. Shima K. J. Am. Chem. Soc.  1989,  111:  3707 
• 1b Ue M. Ohnishi Y. Kobiro K. Kakiuchi K. Tobe Y. Odaira Y. Chem. Lett.  1990,  149 
• 1c Kakiuchi K. Hirao N. Shimizu T. Suwa M. Kobiro K. Tobe Y. Odaira Y. Bull. Chem. Soc. Jpn.  1990,  63:  3039 
• 1d Kakiuchi K. Ohnishi Y. Kobiro K. Tobe Y. Odaira Y. J. Org. Chem.  1991,  56:  463 
• 2 Duk DKM. Fetizon M. Hanna I. Lazare S. Synthesis  1981,  139 
• 3 Duk DKM. Fetizon M. Hanna I. Olesker A. J. Chem. Soc., Chem. Commun.  1980,  1209 
• 4a Kakiuchi K. Fukunaga K. Matsuo F. Ohnishi Y. Tobe Y. J. Org. Chem.  1991,  56:  6742 
• 4b Kakiuchi K. Nakamura I. Matsuo F. Nakata M. Ogura M. Tobe Y. Kurosawa H. J. Org. Chem.  1995,  60:  3318 
• 5 Kakiuchi K. Horiguchi T. Minato K. Tobe Y. Kurosawa H. J. Org. Chem.  1995,  60:  6557 
• 7 For the strength of Lewis acids, see: Cook D. Can. J. Chem.  1963,  41:  522 
• 8 For total synthesis of pentalenene, see: Paquette LA. Geng F. Org. Lett.  2002,  4:  4547 ; and references therein.
• 9 Paquette LA. Annis GD. J. Am. Chem. Soc.  1983,  105:  7358 
• 10 Paquette LA. Pierre F. Cottrell CE. J. Am. Chem. Soc.  1987,  109:  5731 
• 11 Aumiller JC. Whittle JA. J. Org. Chem.  1976,  41:  2955 

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See ref. [1a]