Sweeney, Joseph B. and Ball, Anthony and Lawrence, Philippa and Sinclair, Mackenzie and Smith, Luke (2018) A simple, broad-scope nickel(0) precatalyst system for direct amination of allyl alcohols. Angewandte Chemie International Edition, 57 (32). pp. 10202-10206. ISSN 1433-7851
Full text not available from this repository.Abstract
The preparation of allylic amines is traditionally accomplished by reactions of amines with reactive electrophiles, such as allylic halides, sulfonates, or oxyphosphonium species; such methods involve hazardous reagents, generate stoichiometric waste streams, and often suffer from side reactions (such as overalkylation). We report here the first broad‐scope nickel‐catalysed direct amination of allyl alcohols: An inexpensive NiII/Zn couple enables the allylation of primary, secondary, and electron‐deficient amines without the need for glove‐box techniques. Under mild conditions, primary and secondary aliphatic amines react smoothly with a range of allyl alcohols, giving secondary and tertiary amines efficiently. This “totally catalytic” method can also be applied to electron‐deficient nitrogen nucleophiles; the practicality of the process was demonstrated in an efficient, gram‐scale preparation of the calcium antagonist drug substance flunarizine (Sibelium®).