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Steroids, XXXVII. Neighbouring Group Participation, VIII 2) Neighbouring Group Participation in the 16‐Hydroxymethyl‐3‐methoxyestra‐1,3,5(10)‐trien‐17β‐ol Series
Author(s) -
Schneider Gyula,
Vincze Irén,
Vass András,
Sohár Pál
Publication year - 1988
Publication title -
liebigs annalen der chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 0170-2041
DOI - 10.1002/jlac.198819880315
Subject(s) - solvolysis , chemistry , acetic acid , hydroxymethyl , medicinal chemistry , group (periodic table) , methanol , stereochemistry , organic chemistry , hydrolysis
Abstract Reduction of the acetoxymethylene ketone 1b yielded a mixture of two epimeric diols 3a and 4a , which were converted into the p ‐toluenesulfonates 3d and 4d . Solvolysis of 3d in dry acetic acid afforded 5b after inversion at C‐17. As an explanation for the formation of 5b , it was assumed that the cyclic cation 8 may be an intermediate. This was confirmed by methanolysis of 3d leading to the orthoester 10 . The neighbouring group participation (AcO‐6) observed during solvolysis of 3d was completely absent in the case of 4d , solvolysis of which yielded 17β‐acetoxy‐16α‐acetoxymethyl‐3‐methoxyestra‐1,3,5(10)‐triene ( 4b ) with retention in both acetic acid and methanol.