Thiol-yne reaction
The thiol-yne reaction (also known as alkyne hydrothiolation) is an organic reaction between a thiol and an alkyne. The reaction product is an alkenyl sulfide.[1][2] The reaction was first reported in 1949 with thioacetic acid as reagent[3][4] and rediscovered in 2009.[5] It is used in click chemistry[6][7][8] and in polymerization, especially with dendrimers.
 |
| Thiol-yne reaction |
|---|
This addition reaction is typically facilitated by a radical initiator or UV irradiation 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.[9][10] With diaddition the 1,2-disulfide or the 1,1- dithioacetal forms. Reported catalysts for radical additions are triethylborane,[11] indium(III) bromide[12] and AIBN.[13] The reaction is also reported to be catalysed by cationic rhodium and iridium complexes,[14] by thorium and uraniumcomplexes,[15] by rhodium complexes,[16][17][18] by caesium carbonate[19] and by gold.[20]
 |
| Ichinose et al. thiol-yne reaction 1987[11] |
|---|
Diphenyl disulfide reacts with alkynes to a 1,2-bis(phenylthio)ethylene.[21] Reported alkynes are ynamides.[22] A photoredox thiol-yne reaction has been reported.[23]
Polymer chemistry[edit]
In polymer chemistry, systems have been described based on addition polymerization with 1,4-benzenedithiol and 1,4-diethynylbenzene,[24][25] in the synthesis of other addition polymer systems[26] in the synthesis of dendrimers,[27][28][29][30] in star polymers,[31][32][33][34] in graft polymerization,[35] block copolymers,[36] and in polymer networks.[5][37] Another reported application is the synthesis of macrocycles via dithiol coupling.[38]
https://en.wikipedia.org/wiki/Thiol-yne_reaction
No comments:
Post a Comment