Related Experiment Video
Updated: Mar 5, 2026
08:43
Protocol for the Synthesis of Ortho-trifluoromethoxylated Aniline Derivatives
Published on: January 19, 2016
10.9K
Aryl Fluorosulfate Trapped Staudinger Reduction
Gerui Ren1, Qinheng Zheng, Hua Wang
1Department of Applied Chemistry, School of Food Science and Biotechnology, Zhejiang Gongshang University , Hangzhou 310035, China.
Organic Letters
|March 24, 2017
Summary
A new chemical reaction cascade efficiently links molecules using an aryl sulfamate ester. This method utilizes sulfur(VI) fluoride exchange to trap reactive intermediates, enabling novel synthetic strategies.
Area of Science:
- Organic Chemistry
- Synthetic Chemistry
- Chemical Biology
Background:
- The Staudinger reduction is a common method for converting azides to amines.
- Sulfur(VI) fluoride exchange (SuFEx) chemistry offers unique reactivity for forming stable linkages.
- Developing efficient methods for constructing aryl sulfamate esters is crucial for medicinal chemistry and materials science.
Purpose of the Study:
- To develop a novel chemoselective cascade reaction.
- To establish a new method for forming aryl sulfamate ester linkages.
- To explore the utility of aryl fluorosulfate as an electrophilic trap in Staudinger reduction.
Main Methods:
- A one-pot Staudinger reduction followed by sulfur(VI) fluoride exchange (SuFEx) cascade reaction.
- Utilizing aryl fluorosulfate as a key electrophilic trapping agent for in situ generated iminophosphoranes.
- Synthesis and characterization of various aryl sulfamate esters derived from azide-containing compounds.
Main Results:
- Successfully developed a chemoselective Staudinger reduction/SuFEx cascade.
- Demonstrated the effective use of aryl fluorosulfate as an electrophilic trap.
- Synthesized ten diverse examples of aryl sulfamate esters, showcasing the broad applicability of the method.
Conclusions:
- The developed cascade reaction provides an efficient and versatile route to aryl sulfamate esters.
- This methodology expands the synthetic toolbox for constructing complex molecules containing sulfamate linkages.
- The Staudinger reduction/SuFEx cascade represents a significant advancement in joining chemical fragments.
![Microwave-assisted One-pot Synthesis of N-succinimidyl-4-[18F]fluorobenzoate [18F]SFB](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F2755.jpg&w=3840&q=50)
Related Concept Videos
01:13Electrophilic Aromatic Substitution: Fluorination and Iodination of Benzene
7.7K
Bromination and chlorination of aromatic rings by electrophilic aromatic substitution reactions are easily achieved, but fluorination and iodination are difficult to achieve. Fluorine is so reactive that its reaction with benzene is difficult to control, resulting in poor yields of monofluoroaromatic products. To address this, Selectfluor reagent is used as a fluorine source in which a fluorine atom is bonded to a positively charged nitrogen.
7.7K
01:29Atomic Fluorescence Spectroscopy
1.0K
Atomic fluorescence spectroscopy (AFS) is an analytical technique that involves the electronic transitions of atoms in a flame, furnace, or plasma being excited by electromagnetic (EM) radiation. When these atoms absorb energy, they become excited and subsequently release energy as they return to their original state. This emitted light, or "fluorescence," is observed at a right angle to the incident beam. Both absorption and emission processes transpire at distinct wavelengths, which...
1.0K
01:19Acid Halides to Alcohols: LiAlH4 Reduction
4.2K
Acid halides are reduced to alcohols in the presence of a strong reducing agent like lithium aluminum hydride.
The mechanism proceeds in three steps. First, the nucleophilic hydride ion attacks the carbonyl carbon of the acid halide to form a tetrahedral intermediate. Next, the carbonyl group is re-formed, and the halide ion departs as a leaving group, generating an aldehyde. A second nucleophilic attack by the hydride yields an alkoxide ion, which, upon protonation, gives a primary alcohol as...
The mechanism proceeds in three steps. First, the nucleophilic hydride ion attacks the carbonyl carbon of the acid halide to form a tetrahedral intermediate. Next, the carbonyl group is re-formed, and the halide ion departs as a leaving group, generating an aldehyde. A second nucleophilic attack by the hydride yields an alkoxide ion, which, upon protonation, gives a primary alcohol as...
4.2K
02:23Alcohols from Carbonyl Compounds: Reduction
12.8K
Reduction is a simple strategy to convert a carbonyl group to a hydroxyl group. The three major pathways to reduce carbonyls to alcohols are catalytic hydrogenation, hydride reduction, and borane reduction.
Catalytic hydrogenation is similar to the reduction of an alkene or alkyne by adding H2 across the pi bond in the presence of transition metal catalysts like Raney Ni, Pd–C, Pt, or Ru. Aldehydes and ketones can be reduced by this method, often under mild to moderate heat (25–100°C) and...
Catalytic hydrogenation is similar to the reduction of an alkene or alkyne by adding H2 across the pi bond in the presence of transition metal catalysts like Raney Ni, Pd–C, Pt, or Ru. Aldehydes and ketones can be reduced by this method, often under mild to moderate heat (25–100°C) and...
12.8K
01:20Diazonium Group Substitution with Halogens and Cyanide: Sandmeyer and Schiemann Reactions
2.6K
Arenediazonium substitution reactions occur when the diazonium group is substituted by various functional groups such as halides, hydroxyl, nitrile, etc. For instance, arenediazonium salts react with copper(I) salts of chloride, bromide, or cyanide to form corresponding aryl chlorides, bromides, and nitriles. These reactions are named Sandmeyer reactions. Although the mechanism of this reaction is complicated, as illustrated in Figure 1, they are believed to progress via an aryl copper...
2.6K
02:33Preparation and Reactions of Thiols
7.8K
Thiols are prepared using the hydrosulfide anion as a nucleophile in a nucleophilic substitution reaction with alkyl halides. For instance, bromobutane reacts with sodium hydrosulfide to give butanethiol.
7.8K