Abstract
This chapter reviews displacement reactions to prepare amines and ammonium ions that involve nitrogen nucleophiles. The first part presents substitution reactions of halide and sulfonate leaving groups with amines and amine equivalents. Broader leaving group reactivities are noted for certain allylic systems. For example, ester and carbonate derivatives of Baylis–Hillman adduct alcohols are aminated by conjugate addition/elimination pathways. Allyl ethers can be activated by chlorosulfonyl isocyanate (CSI) to produce carbamates by an SNi process. In addition, the activation of alcohols toward displacement by the Mitsunobu reaction and its variants is discussed. The second part covers transition metal-catalyzed allylic aminations. Mechanistic and regiochemical differences between Pd, Rh, and Ir are highlighted. Asymmetric allylic aminations are covered, with examples provided regarding the influence of chiral ligands, nucleophiles, and substrate structure on enantioselectivity. Methods to prepare primary amines by the direct allylation of ammonia and indirectly using ammonia surrogates are included.
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