Transition-Metal-Catalyzed C-C Bond Formation from C-C Activation.

Area of Science:

• Organic Chemistry
• Catalysis
• Synthetic Methodology

Background:

• Carbon-carbon (C-C) single bonds are fundamental in organic chemistry but are thermodynamically and kinetically inert, making their activation challenging.
• Developing efficient strategies for C-C bond cleavage and functionalization is crucial for synthesizing novel molecules and improving reaction economy.
• Transition-metal catalysis offers a powerful approach to overcome the inertness of C-C bonds.

Purpose of the Study:

• To develop efficient transition-metal-catalyzed strategies for C-C bond activation and functionalization.
• To explore the reactivity of various C-C bonds in alcohols, carboxylic acids, and ketones.
• To gain insights into the mechanisms and scope of these C-C bond-forming reactions.

Main Methods:

• Utilized nickel (Ni)- and rhodium (Rh)-catalyzed reactions for C-C bond cleavage and formation.
• Employed readily available substrates like alcohols, carboxylic acids, and ketones.
• Investigated strategies including decarbonylative coupling, directed decarbonylation, group exchange, and chelation-assisted activation.

Main Results:

• Achieved Ni-catalyzed cross-coupling via C-CN cleavage and Rh-catalyzed decarbonylative coupling of carboxylic acids.
• Demonstrated Rh-catalyzed decarbonylation of aryl ketones and group exchange with carboxylic acids.
• Developed Rh-catalyzed C-C bond activation of secondary benzyl alcohols and Ni/Rh-catalyzed cyclization of strained cyclic compounds.

Conclusions:

• Transition-metal-catalyzed C-C bond activation provides a versatile platform for constructing new C-C bonds with improved atom and step economy.
• The developed methods enable the synthesis of conventionally inaccessible molecules through carbon skeleton rearrangement.
• Further research is needed to expand substrate scope and utilize earth-abundant metal catalysts for broader synthetic applications.