Thiol-yne reaction

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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.

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Thiol-yne reaction Thiol-yne-reaction.svg
Thiol-yne reaction
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 uranium complexes, [15] by rhodium complexes, [16] [17] [18] by caesium carbonate [19] and by gold. [20]

Ichinose et al. thiol-yne reaction 1987 Ichinose thiol-yne 1987.svg
Ichinose et al. thiol-yne reaction 1987
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

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]

See also

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References

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  3. ↑ Bader, H.; Cross, L. C.; Heilbron, Ian; Jones, E. R. H. (1949). "132. Researches on acetylenic compounds. Part XVIII. The addition of thiolacetic acid to acetylenic hydrocarbons. The conversion of monosubstituted acetylenes into aldehydes and 1 : 2-dithiols". Journal of the Chemical Society (Resumed): 619. doi:10.1039/JR9490000619.
  4. ↑ Bader, Henry (1956). "23. The addition of thiolacetic acid to ethynylcarbinols and the conversion of the adducts into aldols and ??-unsaturated aldehydes". Journal of the Chemical Society (Resumed): 116–121. doi:10.1039/JR9560000116.
  5. 1 2 Fairbanks, Benjamin D.; Scott, Timothy F.; Kloxin, Christopher J.; Anseth, Kristi S.; Bowman, Christopher N. (2009). "Thiol−Yne Photopolymerizations: Novel Mechanism, Kinetics, and Step-Growth Formation of Highly Cross-Linked Networks". Macromolecules. 42 (1): 211–217. Bibcode:2009MaMol..42..211F. doi:10.1021/ma801903w. PMC   2651690 . PMID   19461871.
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  19. ↑ Kondoh, Azusa; Takami, Kazuaki; Yorimitsu, Hideki; Oshima, Koichiro (2005). "Stereoselective Hydrothiolation of Alkynes Catalyzed by Cesium Base: Facile Access to (Z)-1-Alkenyl Sulfides". The Journal of Organic Chemistry. 70 (16): 6468–73. doi:10.1021/jo050931z. PMID   16050711.
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  22. ↑ Sato, Akinori; Yorimitsu, Hideki; Oshima, Koichiro (2010). "Radical Additions of Arenethiols to Ynamides for the Selective Synthesis of N-[(Z)-2-(Arylsulfanyl)-1-alkenyl]amides". Bulletin of the Korean Chemical Society. 31 (3): 570. doi: 10.5012/bkcs.2010.31.03.570 .
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  30. ↑ Yu, Bing; Chan, Justin W.; Hoyle, Charles E.; Lowe, Andrew B. (2009). "Sequential thiol-ene/thiol-ene and thiol-ene/thiol-yne reactions as a route to well-defined mono and bis end-functionalized poly(N-isopropylacrylamide)". Journal of Polymer Science Part A: Polymer Chemistry. 47 (14): 3544. Bibcode:2009JPoSA..47.3544Y. doi: 10.1002/pola.23436 .
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  32. ↑ Konkolewicz, Dominik; Gaillard, Sylvain; West, Andrew G.; Cheng, Yuen Yap; Gray-Weale, Angus; Schmidt, Timothy W.; Nolan, Steven P.; Perrier, Sébastien (28 March 2011). "Luminescent Hyperbranched Polymers: Combining Thiol-Yne Chemistry with Gold-Mediated C−H Bond Activation". Organometallics. 30 (6): 1315–1318. doi:10.1021/om200103f.
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  34. ↑ Hartlieb, Matthias; Floyd, Thomas; Cook, Alexander B.; Sanchez-Cano, Carlos; Catrouillet, Sylvain; Burns, James A.; Perrier, Sébastien (2017). "Well-defined hyperstar copolymers based on a thiol–yne hyperbranched core and a poly(2-oxazoline) shell for biomedical applications" (PDF). Polymer Chemistry. 8 (13): 2041–2054. doi:10.1039/C7PY00303J.
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