Visible-Light-Mediated (sp ³)Cα-H Functionalization of Ethers Enabled by Electron Donor-Acceptor Complex

Area of Science:

• Organic Chemistry
• Synthetic Chemistry
• Photochemistry

Background:

• C-H amination is crucial for synthesizing nitrogen-containing compounds.
• Existing methods often require harsh conditions or specific substrates.
• Developing milder, more versatile protocols is an ongoing challenge in organic synthesis.

Purpose of the Study:

• To develop a novel visible-light-mediated protocol for C-H amination of cyclic and acyclic ethers.
• To utilize a unique N-bromosuccinamide-tetrahydrofuran electron donor-acceptor complex as an initiator.
• To explore the functionalization of α-diazoketones and dialkyl azodicarboxylates.

Main Methods:

• Visible-light irradiation was employed to drive the reaction.
• A synthetically derived N-bromosuccinamide-tetrahydrofuran complex initiated the process.
• The protocol was applied to readily available ether feedstocks, α-diazoketones, and dialkyl azodicarboxylates.

Main Results:

• Successful C-H amination of cyclic and acyclic ethers was achieved under mild conditions.
• The N-bromosuccinamide-tetrahydrofuran complex demonstrated effectiveness as an initiator.
• The methodology provides a new route for C-N bond construction.

Conclusions:

• A synthetically beneficial visible-light-mediated protocol for C-H amination of ethers has been established.
• This method offers a milder alternative for C-N bond formation.
• The protocol holds potential for extension to C-C bond forming reactions like arylation and allylation.