PCET-mediated deconstructive cross-coupling of aliphatic alcohols

Area of Science:

• Organic Chemistry
• Catalysis
• Photochemistry

Background:

• Aliphatic alcohols are common feedstocks but challenging precursors for C-C bond formation.
• Traditional methods often require harsh conditions or lack functional group tolerance.
• Developing efficient arylation methods for alcohols is crucial for synthetic chemistry.

Purpose of the Study:

• To develop a practical deconstructive arylation of aliphatic alcohols.
• To establish a synergistic photoredox and nickel dual catalytic system for C(sp3)-C(sp2) bond formation.
• To expand the scope of using alcohols as alkyl radical precursors.

Main Methods:

• Utilizing a synergistic photoredox and nickel dual catalytic system.
• Employing proton-coupled electron transfer (PCET) for radical generation via β-scission.
• Optimization of reaction conditions for broad functional group tolerance and chemoselectivity.

Main Results:

• Efficient formation of C(sp3)-C(sp2) bonds between alcohols and aryl halides.
• Successful arylation of challenging tertiary alcohol substrates with good yields.
• Confirmation of the PCET pathway for radical generation using transient absorption spectroscopy.

Conclusions:

• The developed method offers a versatile approach for the deconstructive arylation of alcohols.
• This strategy broadens the utility of alcohols in cross-coupling reactions.
• The synergistic catalysis provides a powerful tool for constructing complex molecular architectures.