Related Experiment Video
Updated: Jul 8, 2026
12:27
Synthesis of Hypervalent Iodonium Alkynyl Triflates for the Application of Generating Cyanocarbenes
Published on: September 8, 2013
Light-triggered hydrogen cyanide (HCN) release from self-immolative cyanohydrin donors
Ally N Stonas1, Michael D Pluth1
1Department of Chemistry and Biochemistry, Materials Science Institute, Knight Campus for Accelerating Scientific Impact, and Institute of Molecular Biology, University of Oregon, Eugene, Oregon 97403-1253, USA. pluth@uoregon.edu.
Chemical Communications (Cambridge, England)
|July 7, 2026
Summary
Researchers developed light-activated molecules to release hydrogen cyanide (HCN), a signaling molecule. New strategies improve HCN release efficiency, broadening its potential applications in chemical biology and medicine.
Area of Science:
- Chemical Biology
- Organic Chemistry
- Biochemistry
Background:
- Hydrogen cyanide (HCN) is recognized as a significant gasotransmitter and bioregulator.
- Understanding HCN's biological roles requires precise control over its release.
- Existing methods for controlled HCN release may have limitations in efficiency or scope.
Purpose of the Study:
- To design and synthesize novel light-triggered donors for controlled hydrogen cyanide release.
- To investigate strategies for enhancing the efficiency of HCN release from these donors.
- To expand the chemical diversity of molecules capable of releasing HCN upon photoactivation.
Main Methods:
- Development of self-immolative cyanohydrin donors based on the 4,5-dimethoxy-o-nitrobenzyl (DMNB) platform.
- Photochemical activation using light to trigger HCN release.
- Implementation of carbonate- and ether-ligated strategies to modulate release kinetics and efficiency.
Main Results:
- Successful synthesis of a series of light-triggered cyanohydrin donors.
- Demonstration of efficient HCN release upon photoactivation.
- Identification of carbonate- and ether-ligated strategies as effective means to increase release efficiency.
Conclusions:
- The developed DMNB-based cyanohydrin donors provide a versatile platform for light-controlled HCN delivery.
- The carbonate- and ether-ligated strategies represent significant advancements in optimizing HCN release.
- This work expands the toolkit for studying HCN's biological functions and developing related therapeutics.
Related Concept Videos
01:32Aldehydes and Ketones with HCN: Cyanohydrin Formation Overview
Cyanohydrins are compounds that contain –CN and –OH groups on the same carbon atom. They are formed by the nucleophilic addition of the cyanide ions to the carbonyl group. Cyanide ions are highly basic and nucleophilic and can be generated from HCN under aqueous conditions. However, since HCN is a weak acid, the number of cyanide ions generated is very small. Hence, a small amount of base or KCN/NaCN is added to HCN to increase the concentration of the cyanide ions in the reaction mixture.
01:10Aldehydes and Ketones with HCN: Cyanohydrin Formation Mechanism
Cyanohydrins are formed when cyanide nucleophiles and carbonyl compounds like aldehydes and ketones react. A strong base, the cyanide ion, catalyzes cyanohydrin formation. The ions are generated from HCN under aqueous conditions. Once the cyanide ions are generated, the first step involves the nucleophilic attack of the cyanide ions on the electrophilic carbonyl carbon. This attack shifts the π electrons from the C=O to the oxygen atom forming the alkoxide ion intermediate. The alkoxide anion...
00:54Radical Formation: Homolysis
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.
02:41Formation of Halohydrin from Alkenes
An alkene, such as propene, reacts with bromine in the presence of water to yield a halohydrin. Halohydrins contain a halogen and a hydroxyl group attached to adjacent carbons. When the halogen is bromine, it is called a bromohydrin, while a chlorohydrin has chlorine as the halogen.
00:55Nitriles to Amines: LiAlH4 Reduction
Nitriles are reduced to amines in the presence of strong reducing agents like lithium aluminum hydride through a typical nucleophilic acyl substitution. The reaction requires two equivalents of the reducing agent. The reducing agent acts as a source of hydride ions.
As shown below, the mechanism involves three steps. Firstly, the hydride ion acting as a nucleophile attacks the nitrile carbon to form an anion. In the second step, a second equivalent of the hydride ion attacks the anion to...
As shown below, the mechanism involves three steps. Firstly, the hydride ion acting as a nucleophile attacks the nitrile carbon to form an anion. In the second step, a second equivalent of the hydride ion attacks the anion to...
01:01Acid Halides to Carboxylic Acids: Hydrolysis
Hydrolysis of acid halides is a nucleophilic acyl substitution reaction in which acid halides react with water to give carboxylic acids. The reaction occurs readily and does not require acid or a base catalyst.
As shown below, the mechanism involves a nucleophilic attack by water at the carbonyl carbon to form a tetrahedral intermediate. This is followed by the reformation of the carbon–oxygen π bond along with the departure of a halide ion. A final proton transfer step yields carboxylic acid...
As shown below, the mechanism involves a nucleophilic attack by water at the carbonyl carbon to form a tetrahedral intermediate. This is followed by the reformation of the carbon–oxygen π bond along with the departure of a halide ion. A final proton transfer step yields carboxylic acid...