The transition metal-catalyzed Mizoroki–Heck reaction is a powerful method to synthesize C–C bonds, allowing access to several important pharmaceuticals. Traditionally free amines have not been compatible with these approaches due to oxidation of the amine by the transition metal or other side reactions. However, the functionalization of unprotected allylamines is particularly attractive due to their prevalence in various biologically active molecules. Herein we report the palladium-catalyzed selective monoarylation of free allylamines using aryl iodides. The strategy works on primary, secondary, and tertiary amines, making it very general. Our monoarylation method is scalable and works on aryl iodides with a variety of substituted arene or heterocycle motifs, including chromophoric substrates.
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This content will become publicly available on June 26, 2025
Electrochemical α ‐Functionalization of N ‐Aryl‐Activated Tertiary Amines
Numerous appropriately substituted pyridyl or phenyl groups serve as a particularly advantageous activation motif for the electrochemical oxidation of amines. Such groups enable a general, mild method for the electrochemical α‐functionalization of tertiary amines across numerous activating groups and amine scaffolds. Notably, the method accommodates an unprecedented range of nucleophile classes, allowing for the introduction of diverse functional groups to the readily prepared amine substrates. The utility of this method is then demonstrated through applications to unsymmetrical bisfunctionalization, site‐selective functionalization of
- NSF-PAR ID:
- 10532692
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Synthesis & Catalysis
- ISSN:
- 1615-4150
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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