S enantiomer is medicinally desirable, whereas the R enantiomer produces harmful health effects. This reaction can produce the S enantiomer with >90% stereoselectivity. Upon recrystallization of the crude product, the optically pure nitrile can be obtained. History Hydrocyanation was first reported by Arthur and Pratt in 1954, when they homogeneously catalyzed the hydrocyanation of linear alkenes. The industrial process for catalytic hydrocyanation of butadiene to adiponitrile was invented by William C. Drinkard. Transhydrocyanation In transhydrocyanation, an equivalent of HCN is transferred from a cyanohydrin, e.g. acetone cyanohydrin, to another HCN acceptor. The transfer is an equilibrium process, initiated by base. The reaction can be driven by trapping reactions or by the use of a superior HCN acceptor, such as an aldehyde. Hydrocyanation of unsaturated carbonyl compounds α,β-unsaturated carbonyl compounds undergo hydrocyanation in the absence of metal catalysts. One manifestation is a special case of the Michael reaction, leading to β-cyanoketones. Another manifestation leads to vinyl cyanohydrins. β-cyano-cyanohydrins are also observed. Reaction conditions allows access to any of these products. (1) Generally acidic conditions favor 1,2-adducts, while basic conditions favor 1,4-adducts. Additions of alkali metal cyanides, for instance, lead exclusively to 1,4-addition. In contrast to alkali metal cyanides and cyanoaluminates, Lewis acidic cyanides, such as TMSCN, favor 1,2-addition. Acetylenic substrates undergo the reaction; however the scope of this reaction is limited and yields are often low. (5) 1,4-Addition to imines has been observed in a few cases, although imines are often base labile. (6) Esters, nitriles and other carbonyl derivatives also undergo conjugative hydrocyanation. When alkali metal cyanides are used, at least partial neutralization of the reaction medium is usually necessary. Neutralization can be accomplished through an acidic group on the substate itself (internal neutralization). or through the addition of an external acid (external neutralization). Acetic acid is commonly used for this purpose, in a procedure pioneered by Lapworth. (7) Conjugative hydrocyanation was used to prepare the steroidal D ring. Diastereoselectivity is generally high in these addition reactions, and the resulting β-cyano carbonyl compounds can be converted to a number of steroidal products. References Carbon-carbon bond forming reactions Addition reactions Organometallic chemistry Homogeneous catalysis Catalysis