Addition of deuterium to carbonyl double bonds

Addition of deuterium to carbonyl double bonds and their nitrogen analogs is accomplished by complex metal hydrides in an increasing number of examples. In this reduction two deuterium atoms are transferred of course, only the deuterium on carbon is firmly bound, and that attached to the hetero atom can be removed in the usual way. Since such reactions can in general be carried out with LiAlD4 in aprotic solvents, the use of lithium aluminum deuteride, LiAlH4,. offers no peculiarities. The necessary LiAlD4, which is extremely sensitive to hydrolysis, is commercially available. It can be conveniently handled as a solution in a dry dialkyl ether or in tetrahydrofuran at temperatures up to ca. 130°. 

LiAlD4 is often applied to the preparation of deuterium-labeled compounds by reduction of C=0 bonds, for example, to the preparation of isobutyl alcohols labeled in the / -, or y-position29,30 and to the reduction of biacetyl to [2,3-D2]-2,3-butanediol.31 Monodeuterated secondary alcohols are also formed by its action on alicyclic ketones,27,32,33 on deuteration of camphor34 formation of the 2-deuterated product is accompanied by that of [3-Dx]-isoborneol, which indicates that enolization occurs under the reaction conditions. 

Dideuterated alcohols can be obtained by reducing carboxylic esters34-37 or carbonyl chlorides38 39 with lithium aluminum deuteride. The following description has been given of the preparation of [l,l-D2]allyl alcohol from acryloyl chloride 39 

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