Preparation of Carbocyclic S-Adenosylazamethionine Accompanied by a Practical Synthesis of (−)-Aristeromycin

Abstract

For the preparation of a carbocyclic nitrogen analogue of S-adenosylmethionine (carba-AdoazaMet, 4), a practical synthesis of (-)-aristeromycin (7) has been developed using variations of literature procedures. This approach called for a stereospecific synthesis of (3aR,6aR)-2,2-dimethyl-3a,6a-dihydrocyclopenta[1,3]dioxol-4-one ((4R, 5R)-4,5-O-isopropylidene-2-cyclopentenone) (8), which was achieved by modifying reported procedures from D-(-)-ribose.

Encephalitozoon cuniculi mRNA Cap (Guanine N-7) Methyltransferase

“…The carbocyclic derivative of aza-AdoMet has a methylene group in lieu of the ribose O-4 atom (Fig. 4) (23). aza-AdoMet and carbocyclic aza-AdoMet were relatively weak inhibitors of Ecm1, with IC 50 values of 100 and 35 M, respectively (Fig.…”

“…3Ј-OMeGTP was from Amersham Biosciences. azaAdoMet and carbocyclic aza-AdoMet were synthesized as described (23).…”

Preparation of Carbocyclic C‐Nucleosides from α‐Chlorooxime Precursor

“…Recently, we reported [30] an optimized synthesis of 1 on the basis of a ring-closing metathesis reaction. [31] Thus, treatment of 1 with vinyl Grignard in the presence of dimethylsulfur copper, as described by Schneller et al, [32] gave optically pure cyclopentanone 2 as a single isomer in 78 % yield (Scheme 1). The incorporation of a vinyl group onto a cyclopentyl ring by 1,4-enone addition is known to be a high-yielding reaction.…”

Click Azide‐Alkyne Cycloaddition for the Synthesis of D‐(–)‐1,4‐Disubstituted Triazolo‐Carbanucleosides

“…Compound 3 was then easily converted to unstable exoolefin 4 following Schneller's method (Scheme 1). [22] This synthetic approach consists in using a vinyl group as a mask for the hydroxymethyl group of carbocyclic nucleosides.…”

“…[22] A THF (40 mL) solution of 4 (4.46 g, 24.5 mmol) was added dropwise to a suspension of LiAlH 4 (1.67 g, 44.1 mmol, 1.8 equiv.) in THF (100 mL) at 0°C under Ar.…”