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.