1258457-19-0Relevant articles and documents
γ- and δ-Hydroxynitriles: Diastereoselective electrophile-dependent alkylations
Mycka, Robert J.,Eckenhoff, William T.,Steward, Omar W.,Barefoot, Nathan Z.,Fleming, Fraser F.
, p. 366 - 376 (2013)
Deprotonating γ- and δ-hydroxynitriles with i-PrMgCl allows highly diastereoselective alkylations controlled by the asymmetry of the remote carbinol stereocenter. Mechanistic experiments are consistent with γ-hydroxynitriles alkylating via a chelated magnesiated nitrile whereas δ-hydroxynitriles favor alkylation from acyclic magnesiated nitriles. Collectively these alkylations; are the first electrophile-dependent alkylations of acyclic nitriles, exhibit a unique influence on the nature of the Grignard used for the deprotonation, and address the challenge of installing quaternary centers in conformationally mobile, acyclic nitriles.
