Turn left and turn right: recent advances in selectivity controlled carbonylation

Area of Science:

• Organic Chemistry
• Catalysis
• Synthetic Methodology

Background:

• Selectivity is crucial in modern organic synthesis for creating complex molecules efficiently.
• Transition-metal-catalyzed carbonylation is a powerful tool using carbon monoxide as a C1 building block.
• Controlling selectivity in carbonylation reactions with multiple reactive sites remains a challenge.

Purpose of the Study:

• To review advances in controlling selectivity in transition-metal-catalyzed carbonylation from 2018 to 2025.
• To highlight methods for achieving divergent synthesis through precise control of carbonylation reactions.
• To demonstrate how catalytic systems, rather than substrate reactivity, dictate selectivity.

Main Methods:

• Summarizing key research advancements in carbonylation selectivity.
• Analyzing the impact of catalytic system manipulation (ligands, bases, additives) on reaction pathways.
• Reviewing applications across diverse substrate classes including alkenes, alkynes, and organohalides.

Main Results:

• Selectivity in carbonylation can be effectively controlled by the catalytic system.
• Ligand engineering is a key strategy for steering reaction pathways.
• Divergent synthesis is achievable, enabling access to diverse products from common starting materials.

Conclusions:

• Catalytic system design offers a general and tunable approach to divergent synthesis via carbonylation.
• Precise control over reaction pathways is possible through strategic manipulation of reaction conditions.
• This approach enhances the synthetic utility of carbonylation for constructing complex molecules.