Copper Catalyzed C–H Sulfonylation of Benzylamines with a Catalytic Transient Directing Group
DOI: 10.14469/hpc/12033 Metadata
Created: 2022-12-16 14:30
Last modified: 2023-07-17 09:41
License: Creative Commons: Public Domain Dedication 1.0
Funding: (none given)
Co-author: James A. Bull
Description
Transient C–H functionalization involves the dynamic in situ generation of a directing group to allow transition metal me-diated cyclometallation and subsequent functionalization steps. To date most examples involve precious metal catalysis, commonly with palladium. Here we report the C(sp2)–H functionalisation of benzylamines using catalytic copper(II) and a catalytic transient directing group. This is the first example of catalytic copper used with a transient directing group. A dual catalytic copper acetate/2-hydroxynicotinaldehyde system enabled effective functionalization of numerous benzylamines via a transiently formed imine directing group. Manganese(IV) oxide was identified as an effective terminal oxidant and base for this transformation, enabling a diverse array of sulfinate salts and benzylamines to be coupled in good yields. Mechanistic and computational DFT investigations suggest a turnover limiting C–H activation step.
Members
| DOI | Description |
|---|---|
| 10.14469/hpc/12035 | Amine scope - Transient amine |
| 10.14469/hpc/12034 | Sulfinate Scope - Transient amine |
| 10.14469/hpc/12113 | Derivatisation - Transient amine |
| 10.14469/hpc/12036 | DFT computational data |