(NHC)Ni(II)-Directed Insertions and Higher Substituted Olefin Synthesis from Simple Olefins

Area of Science:

• Organometallic Chemistry
• Catalysis
• Organic Synthesis

Background:

• Controlled olefin insertion is crucial for synthesizing bulk and fine chemicals.
• Developing selective methods for diverse insertion demands is a significant challenge.
• Nickel catalysts are widely studied for olefin synthesis and polymerization.

Purpose of the Study:

• To highlight recent advancements in nickel-catalyzed olefin insertion using N-heterocyclic carbene (NHC) ligands.
• To showcase the use of simple terminal olefins as both donors and acceptors.
• To present a novel method replacing traditional hydroalkenylation reagents.

Main Methods:

• Utilizing tailor-made (NHC)Ni(II) catalysts for redox-neutral catalytic cycles.
• Employing α-olefins as olefin donors and alkenyl sources.
• Investigating catalyst performance through steric and electronic tuning of NHC ligands.

Main Results:

• Achieved high chemo- and regioselective cross-insertion controls.
• Demonstrated regiodivergent insertion and convergent synthesis.
• Enabled synthesis of complex olefins, dienes, and cyclic structures with high enantioselectivity using chiral NHC ligands.

Conclusions:

• NHC-nickel catalysis offers a powerful and green approach for synthesizing diverse olefinic structures.
• The developed methods provide access to valuable chemical feedstocks from simple starting materials.
• This work advances the field of catalytic alkenylation and redox-neutral transformations.