Synthesis of optically pure di- to tetra-substituted cyclopentanes from sugar-derived norbornene derivatives

Article abstract of DOI:10.1016/0008-6215(92)84149-M

The chiral norbornene derivative 2 obtained from Lewis acid-catalyzed reaction of an L-arabinose-derived dienophile 1 and cyclopentadiene was oxidized with OsO₄-NaIO₄ to the dialdehyde 3, a tetrasubstituted cyclopentane. Mild treatment of 3 with [Rh(dppp)₂]Cl [dppp = Ph₂P(CH₂)₃PPh₂] (4) selectively epimerized the aldehyde adjacent to the methoxycarbonyl group to give the epi-aldehyde 8. Under more vigorous conditions, this group was decarbonylated to give the monoaldehyde 11, and more strenuous treatment removed the second aldehyde group to give the didecarbonylated cyclopentane derivative 5. The structure and optical purity of 5 was confirmed by its transformation into (1S,2S)-cyclopentane-1,2-dicarboxylic acid (7). The chiral norbornene derivative 2 obtained from Lewis acid-catalyzed reaction of an L-arabinose-derived dienophile 1 and cyclopentadiene was oxidized with OsO₄-NaIO₄ to the dialdehyde 3, a tetrasubstituted cyclopentane. Mild treatment of 3 with [Rh(dppp)₂]Cl [dppp = Ph₂P(CH₂)₃PPh₂] (4) selectively epimerized the aldehyde adjacent to the methoxycarbonyl group to give the epi-aldehyde 8. Under more vigorous conditions, this group was decarbonylated to give the monoaldehyde 11, and more strenuous treatment removed the second aldehyde group to give the didecarbonylated cyclopentane derivative 5. The structure and optical purity of 5 was confirmed by its transformation into (1S,2S)-cyclopentane-1,2-dicarboxylic acid (7).