A procedure for the partial resolution of 1,3-dimethylallene by asymmetric hydroboration is described. The (-) enantiomer is assigned the R configuration. The stereochemistry of electrophilic addition of mercuric acetate in methanol to optically active 1,3-dimethylallene has been determined by relating the configuration of the dissymmetric aliene to the configuration of the major asymmetric adduct. Similarly, the orientation and stereochemistry of halogen addition to (-)-l,3-dimethylallene in carbon tetrachloride, ether, and methanol have been studied. The results of this work establish that oxymercuration and halogenation of 1,3-dimethylallene under the conditions studied are stereospecific trans additions. These reactions and their stereochemistry are discussed with reference to the types of intermediate cations that may participate.
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