Synthesis, Fragmentation, and Rearrangement Reactions of Annelated Cyclobutylcarbinols­

Abstract

New tricyclic annelated cyclobutylcarbinols are synthesized diastereoselectively. Acid-induced fragmentation and Wagner-Meerwein rearrangement of these alcohols to give bicyclic dienes and annelated norbornanes are reported.

Key words

fused-ring systems - carbocations - rearrangements - ring opening - cycloadditions

References

• 1 Breitmaier E. Terpene   Teubner Studienbücher Chemie; Leipzig: 1999. 
• 2 Lee-Ruff E. Mladenova G. Chem. Rev.  2003,  103:  1449 
• 3 Namyslo JC. Kaufmann DE. Chem. Rev.  2003,  103:  1485 
• 4a Pirrung MC. J. Am. Chem. Soc.  1979,  101:  7130 
• 4b Pirrung MC. J. Am. Chem. Soc.  1981,  103:  82 
• 4c Corey EJ. J. Am. Chem. Soc.  1964,  86:  1652 
• 5a Ranu BC. Sarkar DC. Basu MK. Tetrahedron  1989,  45:  3107 
• 5b Lange GL. Gottardo C. Magn. Reson. Chem.  1996,  34:  660 
• 5c As already mentioned in ref. 5b the photocycloaddition of cyclopentene to 1 yields a mixture of diastereomers with 2a and its cis,syn,cis-isomer in a 9:1 ratio. For more details see: Grota J. PhD Thesis   University of Bielefeld; Germany: 2004.  44. p.158 
• 7 Sullivan BW. Faulkner DJ. J. Org. Chem.  1986,  51:  5134 
• 8 Armarego WLF. Perrin DD. In Purification of Laboratory Chemicals   4th ed.:  Butterworth-Heinemann; Oxford: 1996.  p.Chapt. 2 

6

The relative configuration of 2d was determined from 9b by NMR following the reaction sequence 2d Æ 3e Æ 9b.

9

The supplementary crystallographic data for this structure (CCDC 237662) can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, by e-mailing [e-mail], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK.

10

The supplementary crystallographic data for this structure (CCDC 237661) can be obtained free of charge as described in ref. 9.