Related Experiment Video
Updated: May 12, 2025
12:27
Synthesis of Hypervalent Iodonium Alkynyl Triflates for the Application of Generating Cyanocarbenes
Published on: September 8, 2013
10.8K
Iron-Catalyzed Tunable Alkene Migratory Silylation and Transposition
Bohao Guo1, Yu Pu2, Ruichen Zhang2
1Chongqing Key Laboratory of Natural Product Synthesis and Drug Research, School of Pharmaceutical Sciences, Chongqing University, Chongqing 401331, P. R. China.
Organic Letters
|May 9, 2025
Summary
Iron catalysis enables efficient synthesis of allylsilanes and alkenes through migratory silylation and transposition. This method offers broad scope, scalability, and functional group tolerance for complex molecule synthesis.
Area of Science:
- Organometallic Chemistry
- Catalysis
- Synthetic Organic Chemistry
Background:
- Migratory silylation and transposition are crucial reactions in organic synthesis.
- Iron catalysis offers a cost-effective and sustainable alternative to precious metal catalysts.
- Developing efficient iron-catalyzed methods for these transformations remains a challenge.
Purpose of the Study:
- To demonstrate iron-catalyzed migratory silylation and transposition of alkenes.
- To develop a tunable synthetic approach for allylsilanes and internal alkenes.
- To investigate the catalytic mechanism and expand the scope of iron-catalyzed reactions.
Main Methods:
- Utilized iron catalysts for alkene migratory silylation and transposition reactions.
- Explored a broad range of alkene substrates and silylating agents.
- Investigated reaction parameters to optimize efficiency and regioselectivity.
- Analyzed reaction intermediates to elucidate the catalytic mechanism.
Main Results:
- Achieved efficient and regioselective synthesis of thermodynamically stable allylsilanes and internal alkenes.
- Demonstrated excellent functional group tolerance and a broad substrate scope.
- Successfully scaled the reaction to gram-scale synthesis.
- Showcased late-stage functionalization of bio-relevant molecules.
- Identified key iron-silyl and iron-hydride intermediates in a relay catalytic mechanism.
Conclusions:
- Established a versatile and efficient iron-catalyzed method for alkene migratory silylation and transposition.
- Provided valuable mechanistic insights into iron-catalyzed coupling reactions.
- Opened new possibilities for developing novel iron-catalyzed transformations.
- Highlighted the potential of iron catalysis in synthesizing complex organic molecules.
Related Concept Videos
02:24Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
7.6K
Introduction
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
7.6K
02:44Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide
9.6K
Alkenes are converted to 1,2-diols or glycols through a process called dihydroxylation. It involves the addition of two hydroxyl groups across the double bond with two different stereochemical approaches, namely anti and syn. Dihydroxylation using osmium tetroxide progresses with syn stereochemistry.
9.6K
02:17Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
3.2K
Catalytic hydrogenation of alkenes is a transition-metal catalyzed reduction of the double bond using molecular hydrogen to give alkanes. The mode of hydrogen addition follows syn stereochemistry.
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
3.2K
02:10Reduction of Alkynes to trans-Alkenes: Sodium in Liquid Ammonia
9.0K
Alkynes can be reduced to trans-alkenes using sodium or lithium in liquid ammonia. The reaction, known as dissolving metal reduction, proceeds with an anti addition of hydrogen across the carbon–carbon triple bond to form the trans product. Since ammonia exists as a gas (bp = −33°C) at room temperature, the reaction is carried out at low temperatures using a mixture of dry ice (sublimes at −78°C) and acetone.
When dissolved in liquid ammonia, an alkali metal,...
When dissolved in liquid ammonia, an alkali metal,...
9.0K
02:36Regioselectivity and Stereochemistry of Hydroboration
8.0K
A significant aspect of hydroboration–oxidation is the regio- and stereochemical outcome of the reaction.
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn...
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn...
8.0K
01:22Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction
1.8K
The radical dimerization of ketones or aldehydes gives vicinal diols through a pinacol coupling reaction. However, the behavior of titanium metals used for the reaction as a source of electrons is unusual. When the reaction is carried out in the presence of titanium, diols can be isolated at low temperatures. Else titanium further reacts with diols, forming alkenes through the McMurry reaction.
1.8K