A Simple, Broad‐Scope Nickel(0) Precatalyst System for the Direct Amination of Allyl Alcohols

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 (su...

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Bibliographic Details
Published in:Angewandte Chemie 2018-08, Vol.130 (32), p.10359-10363
Main Authors: Sweeney, Joseph B., Ball, Anthony K., Lawrence, Philippa A., Sinclair, Mackenzie C., Smith, Luke J.
Format: Article
Language:English
Subjects:
Alcohol
Alcohols
Aliphatic amines
Allyl compounds
Allylierung
Amination
Amines
Aminierung
C-N-Bindungsbildung
Calcium
Catalysis
Chemical reactions
Chemistry
Halides
Hazardous wastes
Nachhaltige Chemie
Nickel
Nucleophiles
Reagents
Side reactions
Sulfonates
Waste management
Waste streams
Zinc
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Summary: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®). Komplett katalytisch: Ein kostengünstiges Nickel(II)/Zink‐System katalysiert die direkte Aminierung von Allylalkoholen mit primären, sekundären und elektronenarmen Aminen, ohne dass ein Handschuhkasten nötig wäre. Verschiedene Allylalkohole wurden so unter milden Reaktionsbedingungen in sekundäre und tertiäre Amine überführt.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.201805611