Synthesis 2000; 2000(6): 817-823
DOI: 10.1055/s-2000-6271
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Chiral Preparation of Polyoxygenated Cyclopentanoids

Hiromi Nakashima* , Masayuki Sato, Takahiko Taniguchi, Kunio Ogasawara
  • *Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan; Fax +81 (22) 2 17 68 45; E-mail:
Further Information

Publication History

Publication Date:
31 December 2000 (online)

A series of polyoxygenated cyclopentanoids, including 2,2-dimethyl-3a,6a-dihydro-4H-cyclopenta[d][1,3]dioxol-4-one, has been prepared in both enantiomeric forms from cyclopentadiene by employing lipase-mediated kinetic resolution as the key step. Thus, cyclopentadiene is first transformed into racemic cis-4-cumyloxycyclopent-2-en-1-ol which is resolved under transesterification conditions in the presence of lipase PS. After transformation into the corresponding tert-butyldimethylsilyl (TBS) ethers, each of the enantiomers is cis-dihydroxylated diastereoselectively from the less hindered face which is transformed into the 2,3-O-isopropylidene-1,4-di-O-protected (trans-1,2 : cis-2,3 : trans-3,4)-1,2,3,4-cyclopentanetetraol. Selective removal of the 1,4-protecting group gives the corresponding 2,3,4-O-protected cyclopentanols which are further transformed into the 2,3,4-O-protected cyclopentanones on oxidation without suffering β-elimination. Exposure of the cyclopentanones to warm acetic acid allows β-elimination to give rise to the dehydration product 2,2-dimethyl-3a,6a-dihydro-4H-cyclopenta[d][1,3]dioxol-4-one having the corresponding chirality without losing their original chiral integrity.