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Nickel-catalyzed cross-coupling reaction preserves stereochemistry via radical rebound mechanism

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New Nickel-Catalyzed Reaction Simplifies Synthesis of Complex Drug Building Blocks

"Simplifying assembly of these structures changes how chemists approach synthesis."
— Senior author Phil Baran

A team of chemists at Scripps Research has developed a novel nickel-catalyzed cross-coupling reaction that allows carbon fragments to be joined together while preserving three-dimensional molecular geometry. The method represents a significant advance for pharmaceutical chemistry, as it simplifies the construction of complex, chiral molecules that are difficult to make with conventional techniques.

Key Advancements

  • High Selectivity and Yields: The reaction achieves 80–96% enantiospecificity and 40–90% yields across pharmaceutically relevant substrates, including piperidine and pyrrolidine scaffolds.
  • Simple, Standard Conditions: No chiral ligands or specialized additives are required, and the reaction runs under standard lab conditions.
  • Gram-Scale Scalability: The process scales to gram quantities and tolerates functional groups such as free amines, olefins, heterocycles, and aryl bromides.

How It Works

The reaction couples a sulfonyl hydrazide with an alkyl halide via short-lived carbon radicals. A "caged radical rebound" mechanism on the nickel center preserves chirality throughout the process.

Dramatic Improvement in Synthetic Efficiency

One piperidine building block that previously required seven steps was produced in a single coupling step at 60% yield with 95% stereoretention—a dramatic improvement in synthetic efficiency.

Publication Details

The research was published in Science.