INVESTIGATIONS ON STEROIDS. XVIII. CHLORIDES AND CYCLIC SULFITES IN THE SERIES OF 3β, 5, 19-TRIHYDROXYETIOCHOLANIC ACID. A CASE OF ASYMMETRIC SULFUR^*1

Abstract

With the aim of preparing steroids of the 19-hydroxypregnane series, 3p ,5,19trihydroxyetiocholanic acid (I) (1) and some of its esters were subjected to various chemical reactions.

Structures and properties of two diastereomeric cyclic sulfites derived from cis‐3,4‐di‐tert‐butylthiolane‐3,4‐diol and thionyl chloride

“…The mixture was treated as described earlier to give the solid residue. 1 13 C NMR (75 MHz, CDCl 3 ) δ 28.3 (broad peak), 38. 9, 60.8, 102.0;IR (KBr) 1309, 1275, 1234, 1137, 828 cm −1 ; MS (FAB) m/z 311 (MH + ).…”

“…It was demonstrated in 1952 that sulfur in sulfites can be a stereogenic center because of its stabletetrahedral geometry [1]. Since then, many cyclic and acyclic sulfites with a stereogenic center have been prepared because of interest in their structures and applications to organic synthesis [2,3].…”

The influence of sulfur configuration in 1H NMR chemical shifts of diasteromeric five‐membered cyclic sulfites

“…The usefulness of sulfur as a synthetic stereogenic center is due to its stable tetrahedral geometry. This was first clearly demonstrated in 1952 when the separation of steroidal epimeric sulfites was reported …”

“…More recent reports have demonstrated the importance of the differential reactivity of epimeric cyclic sulfites in organometallic additions, oxidations, and reactions with enzymes …”

Chiral Organosulfur Compounds

“…and Ehrenstein(141) obtained chiral sulfites for the first time. They found that a mixture of the cyclic diastereomeric sulfites 95, separated by chromatography, is obtained on treatment of 34-5,19-trihydroxyetiocholanate 96 with thionyl chloride in the pyridine.…”