10.1021/jo0501184.s001 Fraser F. Fleming Fraser F. Fleming Subrahmanyam Gudipati Subrahmanyam Gudipati Zhiyu Zhang Zhiyu Zhang Wang Liu Wang Liu Omar W. Steward Omar W. Steward Cyclic Nitriles:  Diastereoselective Alkylations American Chemical Society 2005 diastereoselective counterion lithium alkylation metalated nitriles Diastereoselective lithiated nitriles alkylate 2005-05-13 00:00:00 Dataset https://acs.figshare.com/articles/dataset/Cyclic_Nitriles_Diastereoselective_Alkylations/3286459 Diastereoselective alkylations of metalated conformationally locked 4-<i>tert-</i>butylcyclohexanecarbonitrile are highly diastereoselective with magnesium and copper counterions but only modestly diastereoselective with lithium as the counterion. Selective generation of diverse metalated nitriles is readily achieved through bromine−magnesium, −copper, and −lithium exchange reactions of the corresponding bromonitrile or, for lithium, by deprotonating the parent nitrile with lithium diethylamide. Collectively, high alkylation stereoselectivities correlate with the retentive alkylations of <i>C</i>-metalated nitriles, whereas <i>N</i>-lithiated nitriles alkylate with modest selectivity, reflecting minimal steric differences in the corresponding axial and equatorial electrophile trajectories.