Thiol-yne reaction

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In organic chemistry, the thiol-yne reaction (also known as alkyne hydrothiolation) is an organic reaction between a thiol (−SH) and an alkyne (−C≡CH). The reaction product is an alkenyl sulfide (−CH=CH−S−). [1] [2]

Contents

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 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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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 no other functional groups form a homologous series with the general chemical formula CnH2n−2. Alkynes are traditionally known as acetylenes, although the name acetylene also refers specifically to C2H2, known formally as ethyne using IUPAC nomenclature. Like other hydrocarbons, alkynes are generally hydrophobic.

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<span class="mw-page-title-main">Pauson–Khand reaction</span> Chemical reaction

The Pauson–Khand (PK) reaction is a chemical reaction, described as a [2+2+1] cycloaddition. In it, an alkyne, an alkene, and carbon monoxide combine into a α,β-cyclopentenone in the presence of a metal-carbonyl catalyst Ihsan Ullah Khand (1935–1980) discovered the reaction around 1970, while working as a postdoctoral associate with Peter Ludwig Pauson (1925–2013) at the University of Strathclyde in Glasgow. Pauson and Khand's initial findings were intermolecular in nature, but the reaction has poor selectivity. Some modern applications instead apply the reaction for intramolecular ends.

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In organosulfur chemistry, the thiol-ene reaction is an organic reaction between a thiol and an alkene to form a thioether. This reaction was first reported in 1905, but it gained prominence in the late 1990s and early 2000s for its feasibility and wide range of applications. This reaction is accepted as a click chemistry reaction given the reactions' high yield, stereoselectivity, high rate, and thermodynamic driving force.

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References

  1. ↑ March, Jerry (1985), Advanced Organic Chemistry: Reactions, Mechanisms, and Structure, 3rd edition, New York: Wiley, ISBN   9780471854722, OCLC   642506595
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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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  11. 1 2 Ichinose, Yoshifumi; Wakamatsu, Kuni; Nozaki, Kyoko; Birbaum, Jean-Luc; Oshima, Koichiro; Utimoto, Kiitiro (1987). "Et3B induced radical addition of thiols to acetylenes". Chemistry Letters. 16 (8): 1647–1650. doi:10.1246/cl.1987.1647.
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  14. ↑ Field, Leslie D.; Messerle, Barbara A.; Vuong, Khuong Q.; Turner, Peter (2009). "Rhodium(I) and iridium(I) complexes containing bidentate phosphine-imidazolyl donor ligands as catalysts for the hydroamination and hydrothiolation of alkynes". Dalton Transactions (18): 3599–614. doi:10.1039/b821188d. PMID   19381423.
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  16. ↑ Yang, Jun; Sabarre, Anthony; Fraser, Lauren R.; Patrick, Brian O.; Love, Jennifer A. (2009). "Synthesis of 1,1-Disubstituted Alkyl Vinyl Sulfides via Rhodium-Catalyzed Alkyne Hydrothiolation: Scope and Limitations". The Journal of Organic Chemistry. 74 (1): 182–7. doi:10.1021/jo801644s. hdl: 2429/5534 . PMID   19053611.
  17. ↑ Sabarre, Anthony; Love, Jennifer (2008). "Synthesis of 1,1-Disubstituted Olefins via Catalytic Alkyne Hydrothiolation/Kumada Cross-Coupling". Organic Letters. 10 (18): 3941–4. doi:10.1021/ol8012843. PMID   18702501.
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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.
  20. ↑ Corma, Avelino; González-Arellano, Camino; Iglesias, Marta; Sánchez, Félix (2010). "Efficient synthesis of vinyl and alkyl sulfides via hydrothiolation of alkynes and electron-deficient olefins using soluble and heterogenized gold complexes catalysts". Applied Catalysis A: General. 375: 49–54. doi:10.1016/j.apcata.2009.12.016.
  21. ↑ Benati, Luisa; Montevecchi, Pier Carlo; Spagnolo, Piero (1991). "Free-radical reactions of benzenethiol and diphenyl disulphide with alkynes. Chemical reactivity of intermediate 2-(phenylthio)vinyl radicals". Journal of the Chemical Society, Perkin Transactions 1 (9): 2103. CiteSeerX   10.1.1.1028.9326 . doi:10.1039/P19910002103.
  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 .
  23. ↑ Zalesskiy, Sergey S.; Shlapakov, Nikita S.; Ananikov, Valentine P. (2016). "Visible light mediated metal-free thiol–yne click reaction". Chem. Sci. 7 (11): 6740–6745. doi:10.1039/C6SC02132H. PMC   5355861 . PMID   28451118.
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  28. ↑ Chen, Gaojian; Kumar, Jatin; Gregory, Andrew; Stenzel, Martina H. (2009). "Efficient synthesis of dendrimers via a thiol–yne and esterification process and their potential application in the delivery of platinum anti-cancer drugs". Chemical Communications (41): 6291–3. doi:10.1039/b910340f. PMID   19826698.
  29. ↑ Semsarilar, Mona; Ladmiral, Vincent; Perrier, SéBastien (2010). "Highly Branched and Hyperbranched Glycopolymers via Reversible Addition−Fragmentation Chain Transfer Polymerization and Click Chemistry". Macromolecules. 43 (3): 1438. Bibcode:2010MaMol..43.1438S. doi:10.1021/ma902587r.
  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 .
  31. ↑ Naik, Sandeep S.; Chan, Justin W.; Comer, Christopher; Hoyle, Charles E.; Savin, Daniel A. (2011). "Thiol–yne 'click' chemistry as a route to functional lipid mimetics". Polym. Chem. 2 (2): 303–305. doi:10.1039/C0PY00231C.
  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.
  33. ↑ Brummelhuis, Niels ten; Schlaad, Helmut (2011). "Stimuli-responsive star polymers through thiol–yne core functionalization/crosslinking of block copolymer micelles". Polymer Chemistry. 2 (5): 1180. doi:10.1039/C1PY00002K.
  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.
  35. ↑ Hensarling, Ryan M.; Doughty, Vanessa A.; Chan, Justin W.; Patton, Derek L. (2009). ""Clicking" Polymer Brushes with Thiol-yne Chemistry: Indoors and Out". Journal of the American Chemical Society. 131 (41): 14673–5. doi:10.1021/ja9071157. PMID   19778016.
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  37. ↑ Lang, Mathias; Schade, Alexandra; Bräse, Stefan (2016). "Synthesis of three-dimensional porous hyper-crosslinked polymers via thiol–yne reaction". Beilstein Journal of Organic Chemistry. 12: 2570–2576. doi: 10.3762/bjoc.12.252 . PMC   5238528 . PMID   28144326.
  38. ↑ Zhou, Weidong; Zheng, Haiyan; Li, Yongjun; Liu, Huibiao; Li, Yuliang (17 September 2010). "Synthesis of Sulfuric Macrocycles and a Rotaxane through Thiol-yne Click and Dithiol Coupling Reactions". Organic Letters. 12 (18): 4078–4081. doi:10.1021/ol1014569. PMID   20712302.
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