Activated hydrogens in unsaturated carbonyl compounds

Enolizalion of conjugated or /3,y-unsatiirated enones and dienones in O-deiiterated solvents facilitates the introduction of deuterium labels into positions as far as three and five carbon atoms away from a given ketone function. Exchange of the activated hydrogens in androst-4-en-3-one (12) provides a good illustration of the potential of this method. Saturation of the double bond (section V) in the deuterated enone (13) followed by back exchange of the a-deuteriums (section II-B) proves to be an excellent method for the preparation of 6,6-d2-5a-androstan-3-one (15).  

During the course of base-catalyzed exchange in O-deuterated alcohols, the vinylic hydrogen in the a position to the ketone is replaced by deuterium, in addition to the hydrogens activated by enolization. Thus, under these conditions the exchange of androst-l-en-3-one (16, R = H) gives a trideuterio derivative (18) instead of the expected 4,4-d2 analog (16, R = D). (For other examples see compounds 13, 19, 21, 23, 26 and 27.) Incorporation of this deuterium is due to rapidly reversible alcohol addition (16 -+17) and elimination (17 18) which competes with the enolization step.  

There are many examples in the literature reporting the successful exchange of activated hydrogens in various enones (see compounds 19-25). Complications are encountered with 3/3-hydroxy-5oc-spirost-8(9)-en-ll-one since the exchange of the 14a-hydrogen is accompanied by inversion at this tertiary center (22). Another unusual case occurs during the attempted deutera- 

With dienones exchange of all potentially activated hydrogens is less certain. For example, in alkaline medium, androsta-3,5-dien-7-one (26) undergoes complete exchange, while only the 2,2,4-trideutero derivative 

An extensive study of the A -3-keto steroid system reveals a number of selective exchange reactions. For example, under controlled conditions in the presence of a strong acid catalyst such as deuterium chloride, it is 

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