ENANTIOSELECTIVE SYNTHESIS OF (1R,4S)-1-AMINO-4-(HYDROXYMETHYL)-2-CYCLOPENTENE A PRECURSOR FOR CARBOCYCLIC NUCLEOSIDE SYNTHESIS

Park, KH; Rapoport, H

HERO ID

4947422

Reference Type

Journal Article

Year

1994

HERO ID 4947422
In Press No
Year 1994
Title ENANTIOSELECTIVE SYNTHESIS OF (1R,4S)-1-AMINO-4-(HYDROXYMETHYL)-2-CYCLOPENTENE A PRECURSOR FOR CARBOCYCLIC NUCLEOSIDE SYNTHESIS
Authors Park, KH; Rapoport, H
Journal Journal of Organic Chemistry
Volume 59
Issue 2
Page Numbers 394-399
Abstract (1R,4S)-1-Amino-4-(hydroxymethyl)-2-cyclpentene, an important precursor for the synthesis of carbocyclic nucleosides, has been prepared from D-glucono-delta-lactone in enantiomerically pure form (er > 99/1). The synthesis proceeded from the lactone via the diisopropylidene-2-amino-2-deoxymannonate and hydrolysis of the terminal isopropylidene group. Selective oxidation of the primary alcohol and esterification gave the corresponding mannarate which was deoxygenated at C5. Further transformations by regiospecific eliminative cleavage of the ketal and hydrogenation gave dimethyl (2S,3R)-2-amino-3-hydroxyadipate. Dieckmann cyclization through specific carbanion formation at C5 led to the aminohydroxy(methoxycarbonyl)cyclopentanone which was readily converted in a series of high-yielding steps to the target cyclopentene. Throughout the synthesis, stereo- and regioselectivities were strongly influenced by the sterically demanding 9-phenyl-9-fluorenyl protecting group on nitrogen.
Doi 10.1021/jo00081a019
Wosid WOS:A1994MV01000019
Is Certified Translation No
Dupe Override No
Is Public Yes