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While primary aliphatic amines are ubiquitous in natural products, they are traditionally considered inert to substitution chemistry. This review highlights historical and recent advances in the field of aliphatic deamination chemistry which demonstrate these moieties can be harnessed as valuable C(sp
3
) synthons. Cross-coupling and photocatalyzed transformations proceeding through polar and radical mechanisms are compared with oxidative deamination and other transition metal catalyzed reactions.
This review covers recent and historical aliphatic deaminative functionalization reactions to encourage the use of primary amines as aliphatic building blocks.