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.

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 

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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 

6

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

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 

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.