Reaktion #52556

ord-2b5dfc89a3fe4636b720ac9170827290

Reaktionsgleichung

O=C(O)CO
glycolic acid
Cc1ccc(S(=O)(=O)O)cc1
p-toluenesulfonic acid
O=C(O)CS
mercaptoacetic acid
O=CC(=O)[O-]
glyoxylate
O=C1CSC(C(=O)O)O1
5-oxo-1,3-oxathiolane-2-carboxylic acid

Lösungsmittel

Reaktionsbedingungen

Detaillierte Bedingungen
See reaction.notes.procedure_details.

Aufarbeitung

  1. 1
    SonstigeIn all cases, the 1,3-oxathiolane ring is prepared in one of the following ways

Vorschrift

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.

Quelle

DOI: 10.6084/m9.figshare.5104873.v1Patent: US06855821B2uspto-grants-2005_02