Related Experiment Video
Updated: May 24, 2025
12:27
Synthesis of Hypervalent Iodonium Alkynyl Triflates for the Application of Generating Cyanocarbenes
Published on: September 8, 2013
10.8K
Sulfonyl hydrazides as a general redox-neutral platform for radical cross-coupling
Jiawei Sun1, Áron Péter1, Jiayan He1
1Department of Chemistry, Scripps Research, La Jolla, CA, USA.
Science (New York, N.Y.)
|March 6, 2025
Summary
Sulfonyl hydrazides act as versatile radical precursors for C-C bond formation through redox-neutral cross-couplings. These reactions are efficient, require no external additives, and enable mild late-stage functionalization.
Area of Science:
- Organic Chemistry
- Synthetic Chemistry
Background:
- Sulfonyl hydrazides are stable compounds with potential applications in organic synthesis.
- Reductive arylation of carbonyl compounds is a key transformation in organic chemistry.
Purpose of the Study:
- To demonstrate the utility of sulfonyl hydrazides as versatile radical precursors.
- To develop efficient C-C bond-forming cross-coupling reactions using sulfonyl hydrazides.
Main Methods:
- Utilizing sulfonyl hydrazides as radical precursors in redox-neutral cross-coupling reactions.
- Employing a variety of coupling partners including activated olefins, alkyl halides, and aryl halides.
- Investigating reactions with seven different classes of compounds to form various C-C bonds.
Main Results:
- Successfully achieved seven types of C-C bond-forming cross-couplings, including C(sp3)-C(sp3), C(sp3)-C(sp2), and C(sp3)-C(sp) bonds.
- Demonstrated that sulfonyl hydrazides act as both radical precursors and electron donors, negating the need for exogenous redox additives.
- Established homogeneous, water-compatible, and operationally simple reaction conditions.
Conclusions:
- Sulfonyl hydrazides are highly versatile radical precursors for diverse C-C bond formations.
- The developed methodology offers a streamlined approach to synthesis and mild late-stage functionalization.
- The reactions are efficient, redox-neutral, and do not require external redox mediators.
![[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)
Related Concept Videos
02:26Preparation and Reactions of Sulfides
4.7K
Sulfides are the sulfur analog of ethers, just as thiols are the sulfur analog of alcohol. Like ethers, sulfides also consist of two hydrocarbon groups bonded to the central sulfur atom. Depending upon the type of groups present, sulfides can be symmetrical or asymmetrical. Symmetrical sulfides can be prepared via an SN2 reaction between 2 equivalents of an alkyl halide and one equivalent of sodium sulfide.
4.7K
01:33Radical Reactivity: Intramolecular vs Intermolecular
1.7K
Radical reactions can occur either intermolecularly or intramolecularly. In an intermolecular radical reaction, a nucleophilic radical adds to an electrophilic alkene or vice versa. In such reactions, the radical and generally the alkene, which is also called the radical trap, are two different molecules. Additionally, for such intermolecular reactions to occur, the radical trap must be active, present in an excess concentration, and the radical starting material must have a weak...
1.7K
01:16Radical Reactivity: Nucleophilic Radicals
2.0K
Radicals adjacent to electron-donating groups are called nucleophilic radicals. These radicals readily react with electrophilic alkenes. The SOMO–LUMO interactions are the driving force for the reaction, where the high-energy SOMO of the electron-rich, nucleophilic radicals interacts with the low-energy LUMO of the electron-deficient, electrophilic alkenes. Such SOMO–LUMO interactions are the basis of reactive radical traps, affecting the selectivity in radical reactions. For...
2.0K
01:11Radical Reactivity: Overview
2.0K
Radicals, the highly reactive species, gain stability by undergoing three different reactions. The first reaction involves a radical-radical coupling, in which a radical combines with another radical, forming a spin‐paired molecule. The second reaction is between a radical and a spin‐paired molecule, generating a new radical and a new spin‐paired molecule. The third reaction is radical decomposition in a unimolecular reaction, forming a new radical and a spin‐paired...
2.0K
00:54Radical Formation: Homolysis
3.5K
A bond is formed between two atoms by sharing two electrons. When this bond is broken by supplying sufficient energy, either two electrons can be taken up by one atom forming ions by the cleavage called heterolysis, or the two electrons are shared by two atoms, with one each creating radicals by the cleavage called homolysis.
3.5K
01:27Radical Substitution: Allylic Bromination
4.9K
In organic synthesis, the formation of products can be altered by changing the reaction conditions. For example, a dibromo addition product is formed when propene is treated with bromine at room temperature. In contrast, propene undergoes allylic substitution in non-polar solvents at high temperatures to give 3-bromopropene. In order to avoid the addition reaction, the bromine concentration must be kept as low as possible throughout the reaction. This can be achieved using N-bromosuccinimide...
4.9K