The thiol-yne reaction (also known as alkyne hydrothiolation) is an

organic reaction Organic reactions are chemical reactions involving organic compounds. The basic organic chemistry reaction types are addition reactions, elimination reactions, substitution reactions, pericyclic reactions, rearrangement reactions, Mechanistic Organ ...

between a

thiol In organic chemistry, a thiol (; ), or thiol derivative, is any organosulfur compound of the form , where R represents an alkyl or other organic substituent. The functional group itself is referred to as either a thiol group or a sulfhydryl gro ...

and an

alkyne \ce \ce Acetylene \ce \ce \ce Propyne \ce \ce \ce \ce 1-Butyne In organic chemistry, an alkyne is an unsaturated hydrocarbon containing at least one carbon—carbon triple bond. The simplest acyclic alkynes with only one triple bond and n ...

. The reaction product is an alkenyl sulfide. The reaction was first reported in 1949 with

thioacetic acid Thioacetic acid is an organosulfur compound with the molecular formula . It is the sulfur analogue of acetic acid (), as implied by the ''thio-'' prefix. It is a yellow liquid with a strong thiol-like odor. It is used in organic synthesis for the ...

as reagent and rediscovered in 2009. It is used in

click chemistry In chemical synthesis, click chemistry is a class of biocompatible small molecule reactions commonly used in bioconjugation, allowing the joining of substrates of choice with specific biomolecules. Click chemistry is not a single specific reaction ...

and in

polymerization In polymer chemistry, polymerization (American English), or polymerisation (British English), is a process of reacting monomer, monomer molecules together in a chemical reaction to form polymer chains or three-dimensional networks. There are ...

, especially with

dendrimer Dendrimers are highly ordered, branched polymeric molecules. Synonymous terms for dendrimer include arborols and cascade molecules. Typically, dendrimers are symmetric about the core, and often adopt a spherical three-dimensional morphology. The ...

s. This

addition reaction In organic chemistry, an addition reaction is, in simplest terms, an organic reaction where two or more molecules combine to form a larger one (the adduct).. Addition reactions are limited to chemical compounds that have multiple bonds, such as ...

is typically facilitated by a

radical initiator In chemistry, radical initiators are substances that can produce radical species under mild conditions and promote radical reactions. These substances generally possess weak bonds—bonds that have small bond dissociation energies. Radical ini ...

UV irradiation Ultraviolet germicidal irradiation (UVGI) is a disinfection method that uses short-wavelength ultraviolet (ultraviolet C or UV-C) light to kill or inactivate microorganisms by destroying nucleic acids and disrupting their DNA, leaving them unabl ...

and proceeds through a sulfanyl radical species. With monoaddition a mixture of (''E''/''Z'')-alkenes form. The mode of addition is anti-Markovnikov. The radical intermediate can engage in secondary reactions such as cyclisation. With diaddition the 1,2-disulfide or the 1,1-

dithioacetal In organosulfur chemistry, thioacetals are the sulfur (''thio-'') analogues of acetals (). There are two classes: the less-common monothioacetals, with the formula , and the dithioacetals, with the formula (symmetric dithioacetals) or (asym ...

forms. Reported catalysts for radical additions are

triethylborane Triethylborane (TEB), also called triethylboron, is an organoborane (a compound with a B–C bond). It is a colorless pyrophoric liquid. Its chemical formula is or , abbreviated . It is soluble in organic solvents tetrahydrofuran and hexane. Pr ...

indium(III) bromide Indium(III) bromide, (indium tribromide), InBr3, is a chemical compound of indium and bromine. It is a Lewis acid and has been used in organic synthesis. Structure It has the same crystal structure as aluminium trichloride, with 6 coordinate ind ...

and AIBN. The reaction is also reported to be catalysed by cationic

rhodium Rhodium is a chemical element with the symbol Rh and atomic number 45. It is a very rare, silvery-white, hard, corrosion-resistant transition metal. It is a noble metal and a member of the platinum group. It has only one naturally occurring isoto ...

and

iridium Iridium is a chemical element with the symbol Ir and atomic number 77. A very hard, brittle, silvery-white transition metal of the platinum group, it is considered the second-densest naturally occurring metal (after osmium) with a density of ...

complexes, by

thorium Thorium is a weakly radioactive metallic chemical element with the symbol Th and atomic number 90. Thorium is silvery and tarnishes black when it is exposed to air, forming thorium dioxide; it is moderately soft and malleable and has a high me ...

and

uranium Uranium is a chemical element with the symbol U and atomic number 92. It is a silvery-grey metal in the actinide series of the periodic table. A uranium atom has 92 protons and 92 electrons, of which 6 are valence electrons. Uranium is weak ...

complexes, by

caesium carbonate Caesium carbonate or cesium carbonate is a white crystalline solid compound. Caesium carbonate has a high solubility in polar solvents such as water, alcohol and DMF. Its solubility is higher in organic solvents compared to other carbonates li ...

and by

gold Gold is a chemical element with the symbol Au (from la, aurum) and atomic number 79. This makes it one of the higher atomic number elements that occur naturally. It is a bright, slightly orange-yellow, dense, soft, malleable, and ductile met ...

Diphenyl disulfide Diphenyl disulfide is the chemical compound with the formula (C6H5S)2. This colorless crystalline material is often abbreviated Ph2S2. It is one of the more commonly encountered organic disulfides in organic synthesis. Minor contamination by thiop ...

reacts with alkynes to a 1,2-bis(phenylthio)ethylene. Reported alkynes are ynamides. A photoredox thiol-yne reaction has been reported.

Polymer chemistry

polymer chemistry Polymer chemistry is a sub-discipline of chemistry that focuses on the structures of chemicals, chemical synthesis, and chemical and physical properties of polymers and macromolecules. The principles and methods used within polymer chemistry are ...

, systems have been described based on

addition polymerization Chain-growth polymerization ( AE) or chain-growth polymerisation ( BE) is a polymerization technique where unsaturated monomer molecules add onto the active site on a growing polymer chain one at a time. There are a limited number of these active ...

with 1,4-benzenedithiol and 1,4-diethynylbenzene, in the synthesis of other addition polymer systems in the synthesis of

s, in

star polymer Star-shaped polymers are the simplest class of branched polymers with a general structure consisting of several (at least three) linear chains connected to a central core. The core, or the center, of the polymer can be an atom, molecule, or macr ...

s, in

graft polymerization In polymer chemistry, graft polymers are segmented copolymers with a linear backbone of one composite and randomly distributed branches of another composite. The picture labeled "graft polymer" shows how grafted chains of species B are covalent ...

block copolymer In polymer chemistry, a copolymer is a polymer derived from more than one species of monomer. The polymerization of monomers into copolymers is called copolymerization. Copolymers obtained from the copolymerization of two monomer species are some ...

s, and in

polymer network In polymer chemistry, branching is the regular or irregular attachment of side chains to a polymer's backbone chain. It occurs by the replacement of a substituent (e.g. a hydrogen atom) on a monomer subunit by another covalently-bonded ch ...

s. Another reported application is the synthesis of macrocycles via dithiol coupling.

References

{{Alkynes Organic reactions

Polymer chemistry

See also

References