1. A Simple, Broad‐Scope Nickel(0) Precatalyst System for the Direct Amination of Allyl Alcohols.
- Author
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Sweeney, Joseph B., Ball, Anthony K., Lawrence, Philippa A., Sinclair, Mackenzie C., and Smith, Luke J.
- Subjects
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CRYSTAL structure , *ELECTROPHILES , *ALLYLATION , *ALIPHATIC amines , *HALIDES - Abstract
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®). [ABSTRACT FROM AUTHOR]
- Published
- 2018
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