| Article ID | Journal | Published Year | Pages | File Type |
|---|---|---|---|---|
| 1349045 | Tetrahedron: Asymmetry | 2010 | 6 Pages |
Starting from (1R,2S,3S,5R)- and (1S,2R,3R,5S)-6,6-dimethylspiro[bicyclo[3.1.1]heptane-2,2’-oxiran]-3-ol (−)-8 and (+)-8, two comparative syntheses were developed for pinane-based chiral carbocyclic nucleosides. The regioselective ring opening of the spiro-oxirane ring of (−)-8 and (+)-8 with NaN3 resulted in azidodiols (−)-9 and (+)-9. Catalytic reduction of (−)-9 and (+)-9 furnished chiral aminodiols (−)-10 and (+)-10, which were transformed by linear synthesis to purine-type nucleosides 16–18 through pyrimidine intermediates. Regioselective ring opening of the oxirane ring of (−)-8 and (+)-8 resulted in adenine-, cytosine- and uracil-based carbocyclic nucleosides 19–21 in a single-step synthesis.
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(1R,2S,3S,5R)-2-(Azidomethyl)-6,6-dimethylbicyclo[3.1.1]heptane-2,3-diolC10H17N3O2[α]D20=-11.0 (c 0.5, MeOH)Source of chirality: (−)-(1S,5S)-α-pineneAbsolute configuration: (1R,2S,3S,5R)
(1R,2S,3S,5R)-2-[(2-Amino-6-chloropyrimidin-4-ylamino)methyl]-6,6-dimethylbicyclo[3.1.1]heptane-2,3-diolC14H21ClN4O22[α]D20=-22.0 (c 0.1, MeOH)Source of chirality(−)-(1S,5S)-α-pineneAbsolute configuration: (1R,2S,3S,5R)
(1R,2S,3S,5R)-2-[(2-Amino-6-chloro-5-((4-chlorophenyl)diazenyl]pyrimidin-4-ylamino)methyl)-6,6-dimethylbicyclo[3.1.1]heptane-2,3-diolC20H24Cl2N6O2[α]D20=+24.0 (c 0.1, MeOH)Source of chirality: (−)-(1S,5S)-α-pineneAbsolute configuration: (1R,2S,3S,5R)
(1R,2S,3S,5R)-2-[(2,5-Diamino-6-chloropyrimidin-4-ylamino)methyl]-6,6-dimethylbicyclo[3.1.1]heptane-2,3-diolC14H22ClN5O2[α]D20=+19.0 (c 0.5, MeOH)Source of chirality: (−)-(1S,5S)-α-pineneAbsolute configuration: (1R,2S,3S,5R)
(1R,2S,3S,5R)-2-[(5-Amino-6-chloropyrimidin-4-ylamino)methyl]-6,6-dimethylbicyclo[3.1.1]heptane-2,3-diolC14H21ClN4O2[α]D20=-15.0 (c 0.1, MeOH)Source of chirality: (−)-(1S,5S)-α-pineneAbsolute configuration: (1R,2S,3S,5R)
(1R,2S,6S,8R)-2-[(6-Chloro-9H-purin-9-yl)methyl]-9,9-dimethyl-4-ethoxy-3,5-dioxatricyclo[6.1.1.02,6]decaneC18H23ClN4O32[α]D20=-124.0 (c 0.155, MeOH)Source of chirality: (−)-(1S,5S)-α-pineneAbsolute configuration: (1R,2S,6S,8R)
(1R,2S,6S,8R)-2-[(6-Hydroxy-9H-purin-9-yl)methyl]-9,9-dimethyl-4-ethoxy-3,5-dioxatricyclo[6.1.1.02,6]decaneC18H24N4O4[α]D20=-18.0 (c 0.1, MeOH)Source of chirality: (−)-(1S,5S)-α-pineneAbsolute configuration: (1R,2S,6S,8R)
(1R,2S,3S,5R)-2-[(6-Hydroxy-9H-purin-9-yl)methyl]-6,6-dimethylbicyclo[3.1.1]heptane-2,3-diol hydrochlorideC15H21ClN2O3[α]D20=-19.0 (c 0.1, MeOH)Source of chirality: (−)-(1S,5S)-α-pineneAbsolute configuration: (1R,2S,3S,5R)
(1R,2S,3S,5R)-2-[(6-Amino-9H-purin-9-yl)methyl]-6,6-dimethylbicyclo[3.1.1]heptane-2,3-diolC15H21N5O2[α]D20=-19.0 (c 0.125, MeOH)Source of chirality: (−)-(1S,5S)-α-pineneAbsolute configuration: (1R,2S,3S,5R)
4-Amino-1-[((1R,2S,3S,5R)-2,3-dihydroxy-6,6-dimethylbicyclo[3.1.1]heptan-2-yl)methyl]pyrimidin-2(1H)-oneC14H21N3O3[α]D20=-17.0 (c 0.125, MeOH)Source of chirality: (−)-(1S,5S)-α-pineneAbsolute configuration: (1R,2S,3S,5R)
1-[(1R,2S,3S,5R)-2,3-Dihydroxy-6,6-dimethylbicyclo[3.1.1]heptan-2-yl)methyl]pyrimidine-2,4(1H,3H)-dioneC14H20N2O4[α]D20=-28.0 (c 0.125, MeOH)Source of chirality: (−)-(1S,5S)-α-pineneAbsolute configuration: (1R,2S,3S,5R)
