ISSN:
0018-019X
Keywords:
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
A new ring expansion method using the cyclofragmentation of epoxysulfones; a synthesis of rac. muscone.Starting from the readily available cyclododecanone 1 the hydroxy sulfone 5 has been prepared using standard procedures. Subsequent dehydration followed by an acidic equilibration resulted in a mixture of two endocyclic olefines, from which the olefin 7 showing the (E)-configuration could be isolated by fractional crystallization. Oxidation of 7 produced the epoxy sulfones 8 and 9. The epoxy sulfone 8 was cyclized to the hydroxy sulfone 10 without any detectable amount of the corresponding epimer 11. Fragmentation of the intermediate 10 using KOTB produced pure (E)-4-muscenone 12. The epoxy sulfone 9 was cyclized to a mixture of the two epimeric hydroxy sulfones 14 and 15. Fragmentation of the two crystalline hydroxy sulfones 14 or 15 with KOTB produced a mixture of 12 and 16. The ‘one-pot’ preparation of (E)-4-muscenone 12 starting from 8 could also be accomplished. The configurational assignements within this serie are based upon the data of an X-ray analysis of the hydroxy sulfone 10.
Additional Material:
7 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/hlca.19760590720
