Iron-Catalyzed Tunable and Site-Selective Olefin Transposition

Area of Science:

• Organic Chemistry
• Catalysis
• Sustainable Chemistry

Background:

• Catalytic isomerization of carbon-carbon double bonds is crucial for synthesizing high-value chemicals.
• Existing methods often lack precise control over double bond migration, especially in complex systems.
• A general catalytic solution for regioselective alkene transposition is highly sought after in the chemical industry.

Purpose of the Study:

• To develop a general catalytic system for controllable alkene transposition.
• To achieve precise control over the position of C═C bond migration in both cyclic and acyclic substrates.
• To enable the synthesis of disubstituted and trisubstituted alkenes with high selectivity.

Main Methods:

• Utilized earth-abundant iron-based complexes as catalysts.
• Employed a base and a boryl compound in conjunction with the iron catalyst.
• Investigated the reaction mechanism involving in situ iron-hydride species formation.

Main Results:

• Demonstrated efficient and controllable alkene transposition using the developed catalytic system.
• Mechanistic studies suggested olefin isomerization via sequential olefin insertion/β-hydride elimination.
• Achieved regiodivergent synthesis, transforming isomeric olefin mixtures into single alkene products.

Conclusions:

• The iron-based catalytic system offers a versatile approach for alkene isomerization.
• This method allows for the transformation of complex olefin mixtures and the synthesis of valuable alkene products.
• The strategy is applicable to biologically active molecules containing unsaturated moieties.