![Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium Under Mild Reaction Conditions](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F51444.jpg&w=3840&q=50)
ROMPgel-supported triphenylphosphine with potential application in parallel synthesis
Erik Arstad1, Anthony G M Barrett, Brian T Hopkins
1Department of Chemistry, Imperial College of Science, Technology and Medicine, London SW7 2AY, United Kingdom.
Organic Letters
|May 25, 2002
Summary
A novel ROMPgel-supported triphenylphosphine reagent was synthesized and demonstrated high efficiency in various organic transformations, including alcohol conversion and Staudinger reactions, offering easy product isolation.
Area of Science:
- Organic Chemistry
- Polymer Chemistry
- Synthetic Chemistry
Background:
- Triphenylphosphine is a versatile reagent in organic synthesis.
- Immobilization of reagents on solid supports facilitates purification and recycling.
- Ring-opening metathesis polymerization (ROMP) offers a route to functionalized polymers.
Purpose of the Study:
- To synthesize a ROMPgel-supported triphenylphosphine reagent.
- To evaluate its performance in key organic reactions.
- To assess the ease of product isolation and reagent recovery.
Main Methods:
- Synthesis of ROMPgel-supported triphenylphosphine via a three-step procedure.
- Characterization of the supported reagent's loading and swelling properties.
- Application in alcohol to halide conversion, ozonide reduction, and Staudinger reactions.
Main Results:
- Successful synthesis of the supported reagent with 67% yield and high loading (2.5 mmol/g).
- Favorable swelling properties in common organic solvents.
- High yields and purity of products obtained after simple filtration and evaporation.
Conclusions:
- ROMPgel-supported triphenylphosphine is an effective and easily handled reagent.
- The supported reagent simplifies reaction workup and purification.
- This methodology offers a greener and more efficient approach to several organic transformations.
Related Concept Videos
01:14Aldehydes and Ketones to Alkenes: Wittig Reaction Mechanism
The Wittig reaction, which converts aldehydes or ketones to alkenes using phosphorus ylides, proceeds through a nucleophilic addition‒elimination process.
The reaction begins with the nucleophilic addition between a phosphorus ylide and the carbonyl compound. Due to its carbanionic character, phosphorus ylide acts as a strong nucleophile and attacks the electrophilic carbonyl group. This generates a charge-separated dipolar intermediate called betaine. The negatively charged oxygen atom and...
The reaction begins with the nucleophilic addition between a phosphorus ylide and the carbonyl compound. Due to its carbanionic character, phosphorus ylide acts as a strong nucleophile and attacks the electrophilic carbonyl group. This generates a charge-separated dipolar intermediate called betaine. The negatively charged oxygen atom and...
01:27Benzene to Phenol via Cumene: Hock Process
The synthesis of phenol from benzene via cumene and cumene hydroperoxide is called the Hock process. First, a Friedel–Crafts alkylation reaction of benzene with propene gives cumene. Then cumene forms cumene hydroperoxide via a radical chain reaction. In the chain initiation step, the benzylic hydrogen is abstracted to give a benzylic radical. In the chain propagation step, the benzylic radical reacts with an oxygen diradical to form a cumene hydroperoxide radical. The cumene hydroperoxide...
01:26Radical Substitution: Hydrogenolysis of Alkyl Halides with Tributyltin Hydride
Radical substitution reactions can be used to remove functional groups from molecules. The hydrogenolysis of alkyl halides is one such reaction, where the weak Sn–H bond in tributyltin hydride reacts with alkyl halides to form alkanes. Here, the reagent Bu3SnH yields tributyltin halide as a byproduct.
The bonds formed in this reaction are stronger than the bonds broken, making it energetically favorable. The reaction follows a radical chain mechanism similar to radical halogenation reactions,...
The bonds formed in this reaction are stronger than the bonds broken, making it energetically favorable. The reaction follows a radical chain mechanism similar to radical halogenation reactions,...
01:16Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)
Ring-opening metathesis polymerization or ROMP involves strained cycloalkenes as starting materials. The mechanism of ROMP proceeds by reacting cycloalkene with Grubbs catalyst to give metallacyclobutane intermediate which undergoes a ring-opening reaction to form new carbene. The new carbene reacts with another molecule of cycloalkene. Repetition of these steps leads to the formation of an unsaturated open-chain polymer product. All these steps are reversible, however, relieving the ring...