Glycolic Acid → 5-Oxo-1,3-oxathiolane-2-carboxylic acid

반응식

[C:1]([O-:5])(=[O:4])[CH:2]=[O:3].C(O)(=O)CO.[SH:11][CH2:12][C:13](O)=[O:14].C1(C)C=CC(S(O)(=O)=O)=CC=1>C1(C)C=CC=CC=1>[O:14]=[C:13]1[O:3][CH:2]([C:1]([OH:5])=[O:4])[S:11][CH2:12]1

참가 물질

실험 절차

In all cases, the 1,3-oxathiolane ring is prepared in one of the following ways: (i) reaction of an aldehyde derived from a glyoxylate or glycolic acid with mercaptoacetic acid in toluene in the presence of p-toluenesulfonic acid to give 5-oxo-1,3-oxathiolane-2-carboxylic acid (Kraus, J-L., et al., Synthesis, 1991, 1046); (ii) cyclization of anhydrous glyoxylates with 2-mercaptoacetaldehyde diethylacetal at reflux in toluene to give 5-ethoxy-1,3-oxathiolane lactone (U.S. Pat. No. 5,047,407); (iii) condensation of glyoxylic acid ester with mercaptoacetaldehyde (dimeric form) to give 5-hydroxy-1,3-oxathiolane-2-carboxylic ester or (iv) coupling of an acyloxyacetaldehyde with 2,5-dihydroxy-1,4-dithiane, the dimeric form of 2-mercaptoacetaldehyde to form a 2-(ayloxy)methyl-5-hydroxy-1,3-oxathiolane. The lactone, 5-oxo compound, has to be reduced to the corresponding lactol during the process to synthesize nucleosides. The 2-carboxylic acid or its ester also has to be reduced to the corresponding 2-hydroxymethyl derivatives with borane-methylsulfide complex.